Detergent compositions containing selected mid-chain branched surfactants

ABSTRACT

Detergent composition comprising a mid-chain branched surfactant and also containing a bleaching agent, aluminosilicate, silicate, and/or detersive enzyme.

CROSS REFERENCE

This is a continuation of PCT International Application Ser. No.PCT/US97/06474, filed Apr. 16, 1997; which claims priority toProvisional Application Ser. Nos. 60/015,521, filed Apr. 16, 1996;60/015,523, filed Apr. 16, 1996; and 60/031,844, filed Nov. 26, 1996 anda divisional of 09/170,185 filed Oct. 13, 1998 now U.S. Pat. No.6,015,781.

FIELD OF THE INVENTION

The present invention relates to a detergent composition comprising amid-chain branched surfactant and a bleaching agent, aluminosilicateand/or silicate builder, and/or detersive enzyme, preferably in granularform. More particularly, the invention is directed to detergentcompositions containing a bleaching agent, aluminosilicate, silicate,and/or detersive enzyme and a selected mid-chain branched surfactant.

BACKGROUND OF THE INVENTION

Most conventional detergent compositions contain mixtures of variousdetersive surfactant components. Commonly encountered surfactantcomponents include various anionic surfactants, especially the alkylbenzene sulfonates, alkyl sulfates, alkyl alkoxy sulfates and variousnonionic surfactants, such as alkyl ethoxylates and alkylphenolethoxylates. Surfactants have found use as detergent components capableof the removal of a wide variety of soils and stains. A consistenteffort however is made by detergent manufacturers to improve detersiveproperties of detergent compositions by providing new and improvedsurfactants.

A problem commonly associated with anionic surfactants is theirsensitivity to cold water and/or hard water. It is the surprisingfinding of the present invention that in comparison to known anionicsurfactant components, the mid-chain branched surfactants utilizedherein provide improved cleaning performance, especially for granulardetergent compositions to be used under colder wash water conditionsand/or in hard water. The cleaning results obtained by using thesemid-chain branched surfactants in combination with bleaching agents areparticularly desirable.

An advantage of the present invention is the improved cleaningperformance, over a wide variety of soils and stains, of the detergentcomposition formulated with the mid-chain branched surfactants.

BACKGROUND ART

U.S. Pat. No. 3,480,556 to deWitt, et al., Nov. 25, 1969, EP 439,316,published by Lever Jul. 31, 1991, and EP 684,300, published by LeverNov. 29, 1995, describe beta-branched alkyl sulfates. EP 439,316describes certain laundry detergents containing a specific commercialC14/C15 branched primary alkyl sulfate, namely LIAL 145 sulfate. This isbelieved to have 61% branching in the 2-position; 30% of this involvesbranching with a hydrocarbon chain having four or more carbon atoms.U.S. Pat. No. 3,480,556 describes mixtures of from 10 to 90 parts of astraight chain primary alkyl sulfate and from 90 to 10 parts of a betabranched (2-position branched) primary alcohol sulfate of formula:##STR1## wherein the total number of carbon atoms ranges from 12 to 20and R1 is a straight chain alkyl radical containing 9 to 17 carbon atomsand R2 is a straight chain alkyl radical containing 1 to 9 carbon atoms(67% 2-methyl and 33% 2-ethyl branching is exemplified).

As noted hereinbefore, R. G. Laughlin in "The Aqueous Phase Behavior ofSurfactants", Academic Press, N.Y. (1994) p. 347 describes theobservation that as branching moves away from the 2-alkyl positiontowards the center of the alkyl hydrophobe there is a lowering of Kraffttemperatures. See also Finger et al., "Detergent alcohols--the effect ofalcohol structure and molecular weight on surfactant properties", J.Amer. Oil Chemists' Society, Vol. 44, p. 525 (1967) and TechnicalBulletin, Shell Chemical Co., S.C.: 364-80.

EP 342,917 A, Unilever, published Nov. 23, 1989 describes laundrydetergents containing a surfactant system in which the major anionicsurfactant is an alkyl sulfate having an assertedly "wide range" ofalkyl chain lengths (the experimental appears to involve mixing coconutand tallow chain length surfactants).

U.S. Pat. No. 4,102,823 and GB 1,399,966 describe other laundrycompositions containing conventional alkyl sulfates.

G.B. Patent 1,299,966, Matheson et al., published Jul. 2, 1975,discloses a detergent composition in which the surfactant system iscomprised of a mixture of sodium tallow alkyl sulfate and nonionicsurfactants.

Methyl-substituted sulfates include the known "isostearyl" sulfates;these are typically mixtures of isomeric sulfates having a total of 18carbon atoms. For example, EP 401,462 A, assigned to Henkel, publishedDec. 12, 1990, describes certain isostearyl alcohols and ethoxylatedisostearyl alcohols and their sulfation to produce the correspondingalkyl sulfates such as sodium isostearyl sulfate. See also K. R. Wormuthand S. Zushma, Langmuir, Vol. 7, (1991), pp 2048-2053 (technical studieson a number of branched alkyl sulfates, especially the "branchedGuerbet" type); R. Varadaraj et al., J. Phys. Chem., Vol. 95, (1991), pp1671-1676 (which describes the surface tensions of a variety of "linearGuerbet" and "branched Guerbet"--class surfactants including alkylsulfates); Varadaraj et al., J. Colloid and Interface Sci., Vol. 140,(1990), pp 31-34 (relating to foaming data for surfactants which includeC12 and C13 alkyl sulfates containing 3 and 4 methyl branches,respectively); and Varadaraj et al., Langmuir, Vol. 6 (1990), pp1376-1378 (which describes the micropolarity of aqueous micellarsolutions of surfactants including branched alkyl sulfates).

"Linear Guerbet" alcohols are available from Henkel, e.g., EUTANOL G-16.

Primary akyl sulfates derived from alcohols made by Oxo reaction onpropylene or n-butylene oligomers are described in U.S. Pat. No.5,245,072 assigned to Mobil Corp. See also: U.S. Pat. No. 5,284,989,assigned to Mobil Oil Corp. (a method for producing substantially linearhydrocarbons by oligomerizing a lower olefin at elevated temperatureswith constrained intermediate pore siliceous acidic zeolite), and U.S.Pat. Nos. 5,026,933 and 4,870,038, both to Mobil Oil Corp. (a processfor producing substantially linear hydrocarbons by oligomerizing a lowerolefin at elevated temperatures with siliceous acidic ZSM-23 zeolite).

See also: Surfactant Science Series, Marcel Dekker, N.Y. (variousvolumes include those entitled "Anionic Surfactants" and "SurfactantBiodegradation", the latter by R. D. Swisher, Second Edition, publ. 1987as Vol. 18; see especially p.20-24 "Hydrophobic groups and theirsources"; pp 28-29 "Alcohols", pp 34-35 "Primary Alkyl Sulfates" and pp35-36 "Secondary Alkyl Sulfates"); and literature on "higher" or"detergent" alcohols from which alkyl sulfates are typically made,including: CEH Marketing Research Report "Detergent Alcohols" by R. F.Modler et al., Chemical Economics Handbook, 1993, 609.5000-609.5002;Kirk Othmer's Encyclopedia of Chemical Technology, 4th Edition, Wiley,N.Y., 1991, "Alcohols, Higher Aliphatic" in Vol. 1, pp 865-913 andreferences therein.

SUMMARY OF THE INVENTION

According to the present invention there is provided a bleachingdetergent composition comprising:

a) from about 0.1% to about 50% by weight of a bleaching agent;

b) from about 0.1% to about 50% by weight of a mid-chain branchedsurfactant selected from the group consisting of surfactants having theformula:

    A.sup.b --CH.sub.2 --B

wherein:

(i) A^(b) is a hydrophobic C9 to C22 (total carbons in the moiety),preferably from about C12 to about C18, mid-chain branched alkyl moietyhaving: (1) a longest linear carbon chain attached to the --X--B moietyin the range of from 8 to 21 carbon atoms; (2) one or more C₁ -C₃ alkylmoieties branching from this longest linear carbon chain; (3) at leastone of the branching alkyl moieties is attached directly to a carbon ofthe longest linear carbon chain at a position within the range ofposition 2 carbon (counting from carbon #1 which is attached to the--X--B moiety) to position ω-2 carbon (the terminal carbon minus 2carbons, i.e., the third carbon from the end of the longest linearcarbon chain); and (4) the surfactant composition has an average totalnumber of carbon atoms in the A^(b) --X moiety in the above formulawithin the range of greater than 14.5 to about 17.5 (preferably fromabout 15 to about 17); and

(ii) B is a hydrophilic moiety selected from sulfates, polyoxyalkylene(such as polyoxyethylene and polyoxypropylene), and alkoxylatedsulfates;

c) from about 0.1% to about 99.8% by weight of detergent compositionadjunct ingredients.

The present invention is also directed to granular detergentcompositions comprising:

a) from about 1% to about 80% (preferably from about 3% to about 40%) byweight of a builder selected from the group consisting ofaluminosilicates, silicates, and mixtures thereof;

b) from about 0.1% to about 50% by weight of a mid-chain branchedsurfactant selected from the group consisting of surfactants having theformula:

    A.sup.b --CH.sub.2 --B

wherein:

(i) A^(b) is a hydrophobic C9 to C22 (total carbons in the moiety),preferably from about C12 to about C18, mid-chain branched alkyl moietyhaving: (1) a longest linear carbon chain attached to the --X--B moietyin the range of from 8 to 21 carbon atoms; (2) one or more C₁ -C₃ alkylmoieties branching from this longest linear carbon chain; (3) at leastone of the branching alkyl moieties is attached directly to a carbon ofthe longest linear carbon chain at a position within the range ofposition 2 carbon (counting from carbon #1 which is attached to the--X--B moiety) to position ω-2 carbon (the terminal carbon minus 2carbons, i.e., the third carbon from the end of the longest linearcarbon chain); and (4) the surfactant composition has an average totalnumber of carbon atoms in the A^(b) --X moiety in the above formulawithin the range of greater than 14.5 to about 17.5 (preferably fromabout 15 to about 17); and

(ii) B is a hydrophilic moiety selected from sulfates, polyoxyalkylene(such as polyoxyethylene and polyoxypropylene), and alkoxylatedsulfates; and

c) from about 0.1% to about 99.8% by weight of detergent compositionadjunct ingredients.

The present invention is further directed to detergent compositionscomprising:

a) from about 0.0001% to about 2% by weight of active detersive enzyme(preferably selected from the group consisting of proteases, cellulases,lipases, amylases, peroxidases, and mixtures thereof);

b) from about 0.1% to about 50% by weight of a mid-chain branchedsurfactant selected from the group consisting of surfactants having theformula:

    A.sup.b --CH.sub.2 --B

wherein:

(i) A^(b) is a hydrophobic C9 to C22 (total carbons in the moiety),preferably from about C12 to about C18, mid-chain branched alkyl moietyhaving: (1) a longest linear carbon chain attached to the --X--B moietyin the range of from 8 to 21 carbon atoms; (2) one or more C₁ -C₃ alkylmoieties branching from this longest linear carbon chain; (3) at leastone of the branching alkyl moieties is attached directly to a carbon ofthe longest linear carbon chain at a position within the range ofposition 2 carbon (counting from carbon #1 which is attached to the--X--B moiety) to position ω-2 carbon (the terminal carbon minus 2carbons, i.e., the third carbon from the end of the longest linearcarbon chain); and (4) the surfactant composition has an average totalnumber of carbon atoms in the A^(b) --X moiety in the above formulawithin the range of greater than 14.5 to about 17.5 (preferably fromabout 15 to about 17); and

(ii) B is a hydrophilic moiety selected from sulfates, polyoxyalkylene(such as polyoxyethylene and polyoxypropylene), and alkoxylatedsulfates; and

c) from about 0.1% to about 99.8% by weight of detergent compositionadjunct ingredients.

Preferably, the mid-chain branched surfactant is used in the presentinvention detergent compositions as a component of a surfactant system(i.e., the surfactant system comprises the mid-chain branched surfactantand one or more co-surfactants) wherein the mid-chain branchedsurfactant is present at levels of from about 0.1% to about 50%,preferably from about 1% to about 40%, most preferably from about 2% toabout 30% by weight of the surfactant system. It is to be noted howeverthat higher levels of mid-chain branched surfactant are within thepresent invention.

Preferably, these detergent compositions comprise a surfactant systemfurther comprising one or more co-surfactants selected from: anionicsurfactants, preferably selected from the group of alkyl alkoxylatedsulfates, alkyl sulfates, and/or linear alkyl benzenesulfonatesurfactants; cationic surfactants, preferably selected from quaternaryammonium surfactants; nonionic surfactants, preferably alkylethoxylates, alkyl polyglycolide, and/or amine oxide surfactants;amphoteric surfactants, preferably selected from betaines and/orpolycarboxylates (for example polyglycinates); and zwiterionicsurfactants.

Preferred bleaching detergent compositions comprise oxygen bleachesselected from perborates, percarbonates, and mixtures thereof, morepreferably in combination with bleach activators such asnonanoyloxybenzene sulfonate (NOBS) and tetraacetyl ethylene diamine(TAED) activators, and mixtures thereof Preformed percarboxylic acidbleaching agents may also be used.

Preferred compositions according to the present invention are directedto granular detergent compositions comprising:

a) from about 0.1% to about 50% by weight of a bleaching agent;

b) from about 1% to about 80% by weight of a builder selected from thegroup consisting of aluminosilicates, silicates, and mixtures thereof;

c) from about 0.0001% to about 2% by weight of active detersive enzyme;

d) from about 0.1% to about 50% by weight of a mid-chain branchedsurfactant selected from the group consisting of surfactants having theformula:

    A.sup.b --CH.sub.2 --B

wherein:

(i) A^(b) is a hydrophobic C9 to C22 (total carbons in the moiety),preferably from about C12 to about C18, mid-chain branched alkyl moietyhaving: (1) a longest linear carbon chain attached to the --X--B moietyin the range of from 8 to 21 carbon atoms; (2) one or more C₁ -C₃ alkylmoieties branching from this longest linear carbon chain; (3) at leastone of the branching alkyl moieties is attached directly to a carbon ofthe longest linear carbon chain at a position within the range ofposition 2 carbon (counting from carbon #1 which is attached to the--X--B moiety) to position ω-2 carbon (the terminal carbon minus 2carbons, i.e., the third carbon from the end of the longest linearcarbon chain); and (4) the surfactant composition has an average totalnumber of carbon atoms in the A^(b) --X moiety in the above formulawithin the range of greater than 14.5 to about 17.5 (preferably fromabout 15 to about 17); and

(ii) B is a hydrophilic moiety selected from sulfates, polyoxyalkylene(such as polyoxyethylene and polyoxypropylene), and alkoxylatedsulfates; and

e) from about 0.1% to about 99.8% by weight of detergent compositionadjunct ingredients.

All percentages, ratios and proportions herein are by weight ofingredients used to prepare the finished compositions unless otherwisespecified. All documents cited herein are, in relevant part,incorporated herein by reference.

DETAILED DESCRIPTION OF THE INVENTION

This invention provides detergent compositions which deliver effectivecleaning of soils and stains via use of a mid-chain branched surfactantsurfactant as described herein in combination with one or more of ableaching agent, aluminosilicate, silicate, and/or detersive enzyme,preferably in granular form.

Percarbonate and perborate, which deliver peroxide bleach into the wash,are a cornerstone technology of modern, ultra-compact granular laundrydetergent formulas. Peroxide bleach is very hydrophilic and, while itcannot match the bleaching effectiveness delivered by peracids (formedfor example from peroxide interaction with TAED), it is effective atdecoloration of pigments (e.g., in particulates or beverage stains) andalso can help remove the color from the organic residues associated withbody soils. Unexpectedly, it has now been discovered that compositionscontaining mid-chain branched surfactant surfactants and bleachingagents deliver superior cleaning and whiteness performance.

This invention also provides detergent compositions which delivereffective cleaning of soils and stains by means of bleach activators,preferably hydrophobic bleach activators, used in combination with amid-chain branched surfactant surfactant useful in the presentcompositions and methods. Everyday soil cleaning and whiteness benefitsfor bleach activators and peracids have already been demonstrated. Ithas now been found that detergent and bleach compositions containingmid-chain branched surfactants and bleach activators (includingpreformed peracids) deliver superior cleaning and whiteness performance.

This invention also provides compositions which deliver effectivecleaning of soils and stains via use of bleach catalysts in the presentinvention compositions and methods. Bleach catalysts (characterized bythe presence of at least one transition metal atom) interact withperoxide to form very powerful hydrophilic bleaches. These bleachesdeliver strong benefits on colored hydrophilic stains and hydrophiliceveryday soils (i.e., socks). The catalysts are typically used atextremely low levels in cleaning products. As disclosed herein, productscontaining mid-chain branched surfactants and bleaching agents, withcatalysts, deliver superior cleaning and whiteness performance. It is tobe recognized, however, that historical use of bleach catalysts has beenmade difficult because of concerns about fabric damage (dimanganesecatalysts are known to cause fabric damage), and thus such concerns mustbe considered when formulating compositions according to the presentinvention containing bleach catalysts.

This invention further provides compositions which deliver effectivecleaning of soils and stains via use of builders selected fromaluminosilicates, silicates, and mixtures thereof in the presentinvention compositions in granular form and methods.

In addition, the present invention provides compositions which delivereffective cleaning of soils and stains via use of detersive enzymes inthe present invention compositions and methods.

Mid-chain Branched Surfactant

An essential component of the liquid cleaning compositions of thepresent invention is an mid-chain branched surfactant. The mid-chainbranched surfactant is selected from the following.

The present invention relates to liquid compositions comprisingmid-chain branched surfactant compounds as described herein before. Insuch compositions, certain points of branching (e.g., the location alongthe chain of the R, R¹, and/or R² moieties in the above formula) arepreferred over other points of branching along the backbone of thesurfactant. The formula below illustrates the mid-chain branching range(i.e., where points of branching occur), preferred mid-chain branchingrange, and more preferred mid-chain branching range for mono-methylbranched alkyl A^(b) moieties useful according to the present invention.##STR2## It should be noted that for the mono-methyl substitutedsurfactants these ranges exclude the two terminal carbon atoms of thechain and the carbon atom immediately adjacent to the --X--B group.

The formula below illustrates the mid-chain branching range, preferredmid-chain branching range, and more preferred mid-chain branching rangefor di-methyl substituted alkyl A^(b) moieties useful according to thepresent invention. ##STR3##

The preferred branched surfactant compositions useful in cleaningcompositions according to the present invention are described in moredetail hereinafter.

(1) Mid-chain Branched Primary Alkyl Sulfate Surfactants

The present invention branched surfactant compositions may comprise twoor more mid-chain branched primary alkyl sulfate surfactants having theformula ##STR4##

The surfactant mixtures of the present invention comprise moleculeshaving a linear primary alkyl sulfate chain backbone (i.e., the longestlinear carbon chain which includes the sulfated carbon atom). Thesealkyl chain backbones comprise from 12 to 19 carbon atoms; and furtherthe molecules comprise a branched primary alkyl moiety having at least atotal of 14, but not more than 20, carbon atoms. In addition, thesurfactant mixture has an average total number of carbon atoms for thebranched primary alkyl moieties within the range of from greater than14.5 to about 17.5. Thus, the present invention mixtures comprise atleast one branched primary alkyl sulfate surfactant compound having alongest linear carbon chain of not less than 12 carbon atoms or morethan 19 carbon atoms, and the total number of carbon atoms includingbranching must be at least 14, and further the average total number ofcarbon atoms for the branched primary alkyl chains is within the rangeof greater than 14.5 to about 17.5.

For example, a C16 total carbon primary alkyl sulfate surfactant having13 carbon atoms in the backbone must have 1, 2, or 3 branching units(i.e., R, R¹ and/or R³) whereby total number of carbon atoms in themolecule is at least 16. In this example, the C16 total carbonrequirement may be satisfied equally by having, for example, one propylbranching unit or three methyl branching units.

R, R¹, and R² are each independently selected from hydrogen and C₁ -C₃alkyl (preferably hydrogen or C₁ -C₂ alkyl, more preferably hydrogen ormethyl, and most preferably methyl), provided R, R¹, and R² are not allhydrogen. Further, when z is 1, at least R or R¹ is not hydrogen.

Although for the purposes of the present invention surfactantcompositions the above formula does not include molecules wherein theunits R, R¹, and R² are all hydrogen (i.e., linear non-branched primaryalkyl sulfates), it is to be recognized that the present inventioncompositions may still further comprise some amount of linear,non-branched primary alkyl sulfate. Further, this linear non-branchedprimary alkyl sulfate surfactant may be present as the result of theprocess used to manufacture the surfactant mixture having the requisiteone or more mid-chain branched primary alkyl sulfates according to thepresent invention, or for purposes of formulating detergent compositionssome amount of linear non-branched primary alkyl sulfate may be admixedinto the final product formulation.

Further it is to be similarly recognized that non-sulfated mid-chainbranched alcohol may comprise some amount of the present inventioncompositions. Such materials may be present as the result of incompletesulfation of the alcohol used to prepare the alkyl sulfate surfactant,or these alcohols may be separately added to the present inventiondetergent compositions along with a mid-chain branched alkyl sulfatesurfactant according to the present invention.

M is hydrogen or a salt forming cation depending upon the method ofsynthesis. Examples of salt forming cations are lithium, sodium,potassium, calcium, magnesium, quaternary alkyl amines having theformula ##STR5## wherein R³, R⁴, R⁵ and R⁶ are independently hydrogen,C₁ -C₂₂ alkylene, C₄ -C₂₂ branched alkylene, C₁ -C₆ alkanol, C₁ -C₂₂alkenylene, C₄ -C₂₂ branched alkenylene, and mixtures thereof Preferredcations are ammonium (R³, R⁴, R⁵ and R⁶ equal hydrogen), sodium,potassium, mono-, di-, and trialkanol ammonium, and mixtures thereof.The monoalkanol ammonium compounds of the present invention have R³equal to C₁ -C₆ alkanol, R⁴, R⁵ and R⁶ equal to hydrogen; dialkanolammonium compounds of the present invention have R³ and R⁴ equal to C₁-C₆ alkanol, R⁵ and R⁶ equal to hydrogen; trialkanol ammonium compoundsof the present invention have R³, R⁴ and R⁵ equal to C₁ -C₆ alkanol, R⁶equal to hydrogen. Preferred alkanol ammonium salts of the presentinvention are the mono-, di- and tri-quaternary ammonium compoundshaving the formulas:

    H.sub.3 N.sup.+ CH.sub.2 CH.sub.2 OH, H.sub.2 N.sup.+ (CH.sub.2 CH.sub.2 OH).sub.2, HN.sup.+ (CH.sub.2 CH.sub.2 OH).sub.3.

Preferred M is sodium, potassium and the C₂ alkanol ammonium saltslisted above; most preferred is sodium.

Further regarding the above formula, w is an integer from 0 to 13; x isan integer from 0 to 13; y is an integer from 0 to 13; z is an integerof at least 1; and w+x+y+z is an integer from 8 to 14.

The preferred surfactant mixtures of the present invention have at least0.001%, more preferably at least 5%, most preferably at least 20% byweight, of the mixture one or more branched primary alkyl sulfateshaving the formula ##STR6## wherein the total number of carbon atoms,including branching, is from 15 to 18, and wherein further for thissurfactant mixture the average total number of carbon atoms in thebranched primary alkyl moieties having the above formula is within therange of greater than 14.5 to about 17.5; R¹ and R² are eachindependently hydrogen or C₁ -C₃ alkyl; M is a water soluble cation; xis from 0 to 11; y is from 0 to 11; z is at least 2; and x+y+z is from 9to 13; provided R¹ and R² are not both hydrogen. More preferred arecompositions having at least 5% of the mixture comprising one or moremid-chain branched primary alkyl sulfates wherein x+y is equal to 9 andz is at least 2.

Preferably, the mixtures of surfactant comprise at least 5% of a midchain branched primary alkyl sulfate having R¹ and R² independentlyhydrogen, methyl, provided R¹ and R² are not both hydrogen; x+y is equalto 8, 9, or 10 and z is at least 2. More preferably the mixtures ofsurfactant comprise at least 20% of a mid chain branched primary alkylsulfate having R¹ and R² independently hydrogen, methyl, provided R¹ andR² are not both hydrogen; x+y is equal to 8,9, or 10 and z is at least2.

Preferred detergent compositions according to the present invention, forexample one useful for laundering fabrics, comprise from about 0.001% toabout 99% of a mixture of mid-chain branched primary alkyl sulfatesurfactants, said mixture comprising at least about 5% by weight of twoor more mid-chain branched alkyl sulfates having the formula: ##STR7##or mixtures thereof; wherein M represents one or more cations; a, b, d,and e are integers, a+b is from 10 to 16, d+e is from 8 to 14 andwherein further

when a+b=10, a is an integer from 2 to 9 and b is an integer from 1 to8;

when a+b=11, a is an integer from 2 to 10 and b is an integer from 1 to9;

when a+b=12, a is an integer from 2 to 11 and b is an integer from 1 to10;

when a+b=13, a is an integer from 2 to 12 and b is an integer from 1 to11;

when a+b=14, a is an integer from 2 to 13 and b is an integer from 1 to12;

when a+b=15, a is an integer from 2 to 14 and b is an integer from 1 to13;

when a+b=16, a is an integer from 2 to 15 and b is an integer from 1 to14;

when d+e=8, d is an integer from 2 to 7 and e is an integer from 1 to 6;

when d+e=9, d is an integer from 2 to 8 and e is an integer from 1 to 7;

when d+e=10, d is an integer from 2 to 9 and e is an integer from 1 to9;

when d+e=11, d is an integer from 2 to 10 and e is an integer from 1 to9;

when d+e=12, d is an integer from 2 to 11 and e is an integer from 1 to10;

when d+e=13, d is an integer from 2 to 12 and e is an integer from 1 to11;

when d+e=14, d is an integer from 2 to 13 and e is an integer from 1 to12;

wherein further for this surfactant mixture the average total number ofcarbon atoms in the branched primary alkyl moieties having the aboveformulas is within the range of greater than 14.5 to about 17.5.

Further, the present invention surfactant composition may comprise amixture of branched primary alkyl sulfates having the formula ##STR8##wherein the total number of carbon atoms per molecule, includingbranching, is from 14 to 20, and wherein further for this surfactantmixture the average total number of carbon atoms in the branched primaryalkyl moieties having the above formula is within the range of greaterthan 14.5 to about 17.5; R, R¹, and R² are each independently selectedfrom hydrogen and C¹ -C₃ alkyl, provided R, R¹, and R² are not allhydrogen; M is a water soluble cation; w is an integer from 0 to 13; xis an integer from 0 to 13; y is an integer from 0 to 13; z is aninteger of at least 1; and w+x+y+z is from 8 to 14; provided that whenR² is a C₁ -C₃ alkyl the ratio of surfactants having z equal to 1 tosurfactants having z of 2 or greater is at least about 1:1, preferablyat least about 1:5, more preferably at least about 1:10, and mostpreferably at least about 1:100. Also preferred are surfactantcompositions, when R² is a C₁ -C₃ alkyl, comprising less than about 20%,preferably less than 10%, more preferably less than 5%, most preferablyless than 1%, of branched primary alkyl sulfates having the aboveformula wherein z equals 1.

Preferred mono-methyl branched primary alkyl sulfates are selected fromthe group consisting of: 3-methyl pentadecanol sulfate, 4-methylpentadecanol sulfate, 5-methyl pentadecanol sulfate, 6-methylpentadecanol sulfate, 7-methyl pentadecanol sulfate, 8-methylpentadecanol sulfate, 9-methyl pentadecanol sulfate, 10-methylpentadecanol sulfate, 11-methyl pentadecanol sulfate, 12-methylpentadecanol sulfate, 13-methyl pentadecanol sulfate, 3-methylhexadecanol sulfate, 4-methyl hexadecanol sulfate, 5-methyl hexadecanolsulfate, 6-methyl hexadecanol sulfate, 7-methyl hexadecanol sulfate,8-methyl hexadecanol sulfate, 9-methyl hexadecanol sulfate, 10-methylhexadecanol sulfate, 11-methyl hexadecanol sulfate, 12-methylhexadecanol sulfate, 13-methyl hexadecanol sulfate, 14-methylhexadecanol sulfate, and mixtures thereof.

Preferred di-methyl branched primary alkyl sulfates are selected fromthe group consisting of 2,3-methyl tetradecanol sulfate, 2,4-methyltetradecanol sulfate, 2,5-methyl tetradecanol sulfate, 2,6-methyltetradecanol sulfate, 2,7-methyl tetradecanol sulfate, 2,8-methyltetradecanol sulfate, 2,9-methyl tetradecanol sulfate, 2,10-methyltetradecanol sulfate, 2,11-methyl tetradecanol sulfate, 2,12-methyltetradecanol sulfate, 2,3-methyl pentadecanol sulfate, 2,4-methylpentadecanol sulfate, 2,5-methyl pentadecanol sulfate, 2,6-methylpentadecanol sulfate, 2,7-methyl pentadecanol sulfate, 2,8-methylpentadecanol sulfate, 2,9-methyl pentadecanol sulfate, 2,10-methylpentadecanol sulfate, 2,11-methyl pentadecanol sulfate, 2,12-methylpentadecanol sulfate, 2,13-methyl pentadecanol sulfate, and mixturesthereof.

The following branched primary alkyl sulfates comprising 16 carbon atomsand having one branching unit are examples of preferred branchedsurfactants useful in the present invention compositions:

5-methylpentadecylsulfate having the formula: ##STR9##6-methylpentadecylsulfate having the formula ##STR10##7-methylpentadecylsulfate having the formula ##STR11##8-methylpentadecylsulfate having the formula ##STR12##9-methylpentadecylsulfate having the formula ##STR13##10-methylpentadecylsulfate having the formula ##STR14## wherein M ispreferably sodium.

The following branched primary alkyl sulfates comprising 17 carbon atomsand having two branching units are examples of preferred branchedsurfactants according to the present invention:

2,5-dimethylpentadecylsulfate having the formula: ##STR15##2,6-dimethylpentadecylsulfate having the formula ##STR16##2,7-dimethylpentadecylsulfate having the formula ##STR17##2,8-dimethylpentadecylsulfate having the formula ##STR18##2,9-dimethylpentadecylsulfate having the formula ##STR19##2,10-dimethylpentadecylsulfate having the formula ##STR20## wherein M ispreferably sodium. (2) Mid-chain Branched Primary Alkyl PolyoxyalkyleneSurfactants

The present invention branched surfactant compositions may comprise oneor more mid-chain branched primary alkyl polyoxyalkylene surfactantshaving the formula ##STR21##

The surfactant mixtures of the present invention comprise moleculeshaving a linear primary polyoxyalkylene chain backbone (i.e., thelongest linear carbon chain which includes the alkoxylated carbon atom).These alkyl chain backbones comprise from 12 to 19 carbon atoms; andfurther the molecules comprise a branched primary alkyl moiety having atleast a total of 14, but not more than 20, carbon atoms. In addition,the surfactant mixture has an average total number of carbon atoms forthe branched primary alkyl moieties within the range of from greaterthan 14.5 to about 17.5. Thus, the present invention mixtures compriseat least one polyoxyalkylene compound having a longest linear carbonchain of not less than 12 carbon atoms or more than 19 carbon atoms, andthe total number of carbon atoms including branching must be at least14, and further the average total number of carbon atoms for thebranched primary alkyl chains is within the range of greater than 14.5to about 17.5.

For example, a C16 total carbon (in the alkyl chain) primarypolyoxyalkylene surfactant having 15 carbon atoms in the backbone musthave a methyl branching unit (either R, R¹ or R² is methyl) whereby thetotal number of carbon atoms in the molecule is 16.

R, R¹, and R² are each independently selected from hydrogen and C₁ -C₃alkyl (preferably hydrogen or C ₁ -C₂ alkyl, more preferably hydrogen ormethyl, and most preferably methyl), provided R, R¹, and R² are not allhydrogen. Further, when z is 1, at least R or R¹ is not hydrogen.

Although for the purposes of the present invention surfactantcompositions the above formula does not include molecules wherein theunits R, R¹, and R² are all hydrogen (i.e., linear non-branched primarypolyoxyalkylenes), it is to be recognized that the present inventioncompositions may still further comprise some amount of linear,non-branched primary polyoxyalkylene. Further, this linear non-branchedprimary polyoxyalkylene surfactant may be present as the result of theprocess used to manufacture the surfactant mixture having the requisitemid-chain branched primary polyoxyalkylenes according to the presentinvention, or for purposes of formulating detergent compositions someamount of linear non-branched primary polyoxyalkylene may be admixedinto the final product formulation.

Further it is to be similarly recognized that non-alkoxylated mid-chainbranched alcohol may comprise some amount of the present inventionpolyoxyalkylene-containing compositions. Such materials may be presentas the result of incomplete alkoxylation of the alcohol used to preparethe polyoxyalkylene surfactant, or these alcohols may be separatelyadded to the present invention detergent compositions along with amid-chain branched polyoxyalkylene surfactant according to the presentinvention.

Further regarding the above formula, w is an integer from 0 to 13; x isan integer from 0 to 13; y is an integer from 0 to 13; z is an integerof at least 1; and w+x+y+z is an integer from 8 to 14.

EO/PO are alkoxy moieties, preferably selected from ethoxy, propoxy, andmixed ethoxy/propoxy groups, most preferably ethoxy, wherein m is atleast about 1, preferably within the range of from about 3 to about 30,more preferably from about 5 to about 20, and most preferably from about5 to about 15. The (EO/PO)_(m) moiety may be either a distribution withaverage degree of alkoxylation (e.g., ethoxylation and/or propoxylation)corresponding to m, or it may be a single specific chain withalkoxylation (e.g., ethoxylation and/or propoxylation) of exactly thenumber of units corresponding to m.

The preferred surfactant mixtures of the present invention have at least0.001%, more preferably at least 5%, most preferably at least 20% byweight, of the mixture one or more mid-chain branched primary alkylpolyoxyalkylenes having the formula ##STR22## wherein the total numberof carbon atoms, including branching, is from 15 to 18, and whereinfurther for this surfactant mixture the average total number of carbonatoms in the branched primary alkyl moieties having the above formula iswithin the range of greater than 14.5 to about 17.5; R¹ and R² are eachindependently hydrogen or C₁ -C₃ alkyl; x is from 0 to 11; y is from 0to 11; z is at least 2; and x+y+z is from 9 to 13; provided R¹ and R²are not both hydrogen; and EO/PO are alkoxy moieties selected fromethoxy, propoxy, and mixed ethoxy/propoxy groups, wherein m is at leastabout 1, preferably within the range of from about 3 to about 30, morepreferably from about 5 to about 20, and most preferably from about 5 toabout 15. More preferred are compositions having at least 5% of themixture comprising one or more mid-chain branched primarypolyoxyalkylenes wherein z is at least 2.

Preferably, the mixtures of surfactant comprise at least 5%, preferablyat least about 20%, of a mid chain branched primary alkylpolyoxyalkylene having R¹ and R² independently hydrogen or methyl,provided R¹ and R² are not both hydrogen; x+y is equal to 8, 9 or 10 andz is at least 2.

Preferred detergent compositions according to the present invention, forexample one useful for laundering fabrics, comprise from about 0.001% toabout 99% of a mixture of mid-chain branched primary alkylpolyoxyalkylene surfactants, said mixture comprising at least about 2%by weight of one or more mid-chain branched alkyl polyoxyalkyleneshaving the formula: ##STR23## or mixtures thereof, wherein a, b, d, ande are integers, a+b is from 10 to 16, d+e is from 8 to 14 and whereinfurther

when a+b=10, a is an integer from 2 to 9 and b is an integer from 1 to8;

when a+b=11, a is an integer from 2 to 10 and b is an integer from 1 to9;

when a+b=12, a is an integer from 2 to 11 and b is an integer from 1 to10;

when a+b=13, a is an integer from 2 to 12 and b is an integer from 1 to11;

when a+b=14, a is an integer from 2 to 13 and b is an integer from 1 to12;

when a+b=15, a is an integer from 2 to 14 and b is an integer from 1 to13;

when a+b=16, a is an integer from 2 to 15 and b is an integer from 1 to14;

when d+e=8, d is an integer from 2 to 7 and e is an integer from 1 to 6;

when d+e=9, d is an integer from 2 to 8 and e is an integer from 1 to 7;

when d+e=10, d is an integer from 2 to 9 and e is an integer from 1 to8;

when d+e=11, d is an integer from 2 to 10 and e is an integer from 1 to9;

when d+e=12, d is an integer from 2 to 11 and e is an integer from 1 to10;

when d+e=13, d is an integer from 2 to 12 and e is an integer from 1 to11;

when d+e=14, d is an integer from 2 to 13 and e is an integer from 1 to12;

and wherein further for this surfactant mixture the average total numberof carbon atoms in the branched primary alkyl moieties having the aboveformulas is within the range of greater than 14.5 to about 17.5; andEO/PO are alkoxy moieties selected from ethoxy, propoxy, and mixedethoxy/propoxy groups, wherein m is at least about 1, preferably withinthe range of from about 3 to about 30, more preferably from about 5 toabout 20, and most preferably from about 5 to about 15.

Further, the present invention surfactant composition may comprise amixture of branched primary alkyl polyoxyalkylenes having the formula##STR24## wherein the total number of carbon atoms per molecule,including branching, is from 14 to 20, and wherein further for thissurfactant mixture the average total number of carbon atoms in thebranched primary alkyl moieties having the above formula is within therange of greater than 14.5 to about 17.5; R, R¹, and R² are eachindependently selected from hydrogen and C₁ -C₃ alkyl, provided R, R¹,and R² are not all hydrogen; w is an integer from 0 to 13; x is aninteger from 0 to 13; y is an integer from 0 to 13; z is an integer ofat least 1; w+x+y+z is from 8 to 14; EO/PO are alkoxy moieties,preferably selected from ethoxy, propoxy, and mixed ethoxy/propoxygroups, wherein m is at least about 1, preferably within the range offrom about 3 to about 30, more preferably from about 5 to about 20, andmost preferably from about 5 to about 15; provided that when R² is C₁-C₃ alkyl the ratio of surfactants having z equal to 2 or greater tosurfactants having z of 1 is at least about 1:1, preferably at leastabout 1.5:1, more preferably at least about 3:1, and most preferably atleast about 4:1. Also preferred are surfactant compositions when R² isC₁ -C₃ alkyl comprising less than about 50%, preferably less than about40%, more preferably less than about 25%, most preferably less thanabout 20%, of branched primary alkyl polyoxyalkylene having the aboveformula wherein z equals 1.

Preferred mono-methyl branched primary alkyl ethoxylates are selectedfrom the group consisting of: 3-methyl pentadecanol ethoxylate, 4-methylpentadecanol ethoxylate, 5-methyl pentadecanol ethoxylate, 6-methylpentadecanol ethoxylate, 7-methyl pentadecanol ethoxylate, 8-methylpentadecanol ethoxylate, 9-methyl pentadecanol ethoxylate, 10-methylpentadecanol ethoxylate, 11-methyl pentadecanol ethoxylate, 12-methylpentadecanol ethoxylate, 13-methyl pentadecanol ethoxylate, 3-methylhexadecanol ethoxylate, 4-methyl hexadecanol ethoxylate, 5-methylhexadecanol ethoxylate, 6-methyl hexadecanol ethoxylate, 7-methylhexadecanol ethoxylate, 8-methyl hexadecanol ethoxylate, 9-methylhexadecanol ethoxylate, 10-methyl hexadecanol ethoxylate, 11-methylhexadecanol ethoxylate, 12-methyl hexadecanol ethoxylate, 13-methylhexadecanol ethoxylate, 14-methyl hexadecanol ethoxylate, and mixturesthereof, wherein the compounds are ethoxylated with an average degree ofethoxylation of from about 5 to about 15.

Preferred di-methyl branched primary alkyl ethoxylates selected from thegroup consisting of 2,3-methyl tetradecanol ethoxylate, 2,4-methyltetradecanol ethoxylate, 2,5-methyl tetradecanol ethoxylate, 2,6-methyltetradecanol ethoxylate, 2,7-methyl tetradecanol ethoxylate, 2,8-methyltetradecanol ethoxylate, 2,9-methyl tetradecanol ethoxylate, 2,10-methyltetradecanol ethoxylate, 2,11-methyl tetradecanol ethoxylate,2,12-methyl tetradecanol ethoxylate, 2,3-methyl pentadecanol ethoxylate,2,4-methyl pentadecanol ethoxylate, 2,5-methyl pentadecanol ethoxylate,2,6-methyl pentadecanol ethoxylate, 2,7-methyl pentadecanol ethoxylate,2,8-methyl pentadecanol ethoxylate, 2,9-methyl pentadecanol ethoxylate,2,10-methyl pentadecanol ethoxylate, 2,11-methyl pentadecanolethoxylate, 2,12-methyl pentadecanol ethoxylate, 2,13-methylpentadecanol ethoxylate, and mixtures thereof, wherein the compounds areethoxylated with an average degree of ethoxylation of from about 5 toabout 15.

(3) Mid-chain Branched Primary Alkyl Alkoxylated Sulfate Surfactants

The present invention branched surfactant compositions may comprise oneor more (preferably a mixture of two or more) mid-chain branched primaryalkyl alkoxylated sulfates having the formula: ##STR25##

The surfactant mixtures of the present invention comprise moleculeshaving a linear primary alkoxylated sulfate chain backbone (i.e., thelongest linear carbon chain which includes the alkoxy-sulfated carbonatom). These alkyl chain backbones comprise from 12 to 19 carbon atoms;and further the molecules comprise a branched primary alkyl moietyhaving at least a total of 14, but not more than 20, carbon atoms. Inaddition, the surfactant mixture has an average total number of carbonatoms for the branched primary alkyl moieties within the range of fromgreater than 14.5 to about 17.5. Thus, the present invention mixturescomprise at least one alkoxylated sulfate compound having a longestlinear carbon chain of not less than 12 carbon atoms or more than 19carbon atoms, and the total number of carbon atoms including branchingmust be at least 14, and further the average total number of carbonatoms for the branched primary alkyl chains is within the range ofgreater than 14.5 to about 17.5.

For example, a C16 total carbon (in the alkyl chain) primary alkylalkoxylated sulfate surfactant having 15 carbon atoms in the backbonemust have a methyl branching unit (either R, R¹ or R² is methyl) wherebythe total number of carbon atoms in the primary alkyl moiety of themolecule is 16.

R, R¹, and R² are each independently selected from hydrogen and C₁ -C₃alkyl (preferably hydrogen or C₁ -C₂ alkyl, more preferably hydrogen ormethyl, and most preferably methyl), provided R, R¹, and R² are not allhydrogen. Further, when z is 1, at least R or R¹ is not hydrogen.

Although for the purposes of the present invention surfactantcompositions the above formula does not include molecules wherein theunits R, R¹, and R² are all hydrogen (i.e., linear non-branched primaryalkoxylated sulfates), it is to be recognized that the present inventioncompositions may still further comprise some amount of linear,non-branched primary alkoxylated sulfate. Further, this linearnon-branched primary alkoxylated sulfate surfactant may be present asthe result of the process used to manufacture the surfactant mixturehaving the requisite mid-chain branched primary alkoxylated sulfatesaccording to the present invention, or for purposes of formulatingdetergent compositions some amount of linear non-branched primaryalkoxylated sulfate may be admixed into the final product formulation.

It is also to be recognized that some amount of mid-chain branched alkylsulfate may be present in the compositions. This is typically the resultof sulfation of non-alkoxylated alcohol remaining following incompletealkoxylation of the mid-chain branched alcohol used to prepare thealkoxylated sulfate useful herein. It is to be recognized, however, thatseparate addition of such mid-chain branched alkyl sulfates is alsocontemplated by the present invention compositions.

Further it is to be similarly recognized that non-sulfated mid-chainbranched alcohol (including polyoxyalkylene alcohols) may comprise someamount of the present invention alkoxylated sulfate-containingcompositions. Such materials may be present as the result of incompletesulfation of the alcohol (alkoxylated or non-alkoxylated) used toprepare the alkoxylated sulfate surfactant, or these alcohols may beseparately added to the present invention detergent compositions alongwith a mid-chain branched alkoxylated sulfate surfactant according tothe present invention.

M is as described hereinbefore.

Further regarding the above formula, w is an integer from 0 to 13; x isan integer from 0 to 13; y is an integer from 0 to 13; z is an integerof at least 1; and w+x+y+z is an integer from 8 to 14.

EO/PO are alkoxy moieties, preferably selected from ethoxy, propoxy, andmixed ethoxy/propoxy groups, wherein m is at least about 0.01,preferably within the range of from about 0.1 to about 30, morepreferably from about 0.5 to about 10, and most preferably from about 1to about 5. The (EO/PO)_(m) moiety may be either a distribution withaverage degree of alkoxylation (e.g., ethoxylation and/or propoxylation)corresponding to m, or it may be a single specific chain withalkoxylation (e.g., ethoxylation and/or propoxylation) of exactly thenumber of units corresponding to m.

The preferred surfactant mixtures of the present invention have at least0.001%, more preferably at least 5%, most preferably at least 20% byweight, of the mixture one or more mid-chain branched primary alkylalkoxylated sulfates having the formula ##STR26## wherein the totalnumber of carbon atoms, including branching, is from 15 to 18, andwherein further for this surfactant mixture the average total number ofcarbon atoms in the branched primary alkyl moieties having the aboveformula is within the range of greater than 14.5 to about 17.5; R¹ andR² are each independently hydrogen or C₁ -C₃ alkyl; M is a water solublecation; x is from 0 to 11; y is from 0 to 11; z is at least 2; and x+y+zis from 9 to 13; provided R¹ and R² are not both hydrogen; and EO/PO arealkoxy moieties selected from ethoxy, propoxy, and mixed ethoxy/propoxygroups, wherein m is at least about 0.01, preferably within the range offrom about 0.1 to about 30, more preferably from about 0.5 to about 10,and most preferably from about 1 to about 5. More preferred arecompositions having at least 5% of the mixture comprising one or moremid-chain branched primary alkoxylated sulfates wherein z is at least 2.

Preferably, the mixtures of surfactant comprise at least 5%, preferablyat least about 20%, of a mid chain branched primary alkyl alkoxylatedsulfate having R¹ and R² independently hydrogen or methyl, provided R¹and R² are not both hydrogen; x+y is equal to 8, 9 or 10 and z is atleast 2.

Preferred detergent compositions according to the present invention, forexample one useful for laundering fabrics, comprise from about 0.001% toabout 99% of a mixture of mid-chain branched primary alkyl alkoxylatedsulfate surfactants, said mixture comprising at least about 5% by weightof one or more mid-chain branched alkyl alkoxylated sulfates having theformula: ##STR27## or mixtures thereof; wherein M represents one or morecations; a, b, d, and e are integers, a+b is from 10 to 16, d+e is from8 to 14 and wherein further

when a+b=10, a is an integer from 2 to 9 and b is an integer from 1 to8;

when a+b=11, a is an integer from 2 to 10 and b is an integer from 1 to9;

when a+b=12, a is an integer from 2 to 11 and b is an integer from 1 to10;

when a+b=13, a is an integer from 2 to 12 and b is an integer from 1 to11;

when a+b=14, a is an integer from 2 to 13 and b is an integer from 1 to12;

when a+b=15, a is an integer from 2 to 14 and b is an integer from 1 to13;

when a+b=16, a is an integer from 2 to 15 and b is an integer from 1 to14;

when d+e=8, d is an integer from 2 to 7 and e is an integer from 1 to 6;

when d+e=9, d is an integer from 2 to 8 and e is an integer from 1 to 7;

when d+e=10, d is an integer from 2 to 9 and e is an integer from 1 to8;

when d+e=11, d is an integer from 2 to 10 and e is an integer from 1 to9;

when d+e=12, d is an integer from 2 to 11 and e is an integer from 1 to10;

when d+e=13, d is an integer from 2 to 12 and e is an integer from 1 to11;

when d+e=14, d is an integer from 2 to 13 and e is an integer from 1 to12;

and wherein further for this surfactant mixture the average total numberof carbon atoms in the branched primary alkyl moieties having the aboveformulas is within the range of greater than 14.5 to about 17.5; andEO/PO are alkoxy moieties selected from ethoxy, propoxy, and mixedethoxy/propoxy groups, wherein m is at least about 0.01, preferablywithin the range of from about 0.1 to about 30, more preferably fromabout 0.5 to about 10, and most preferably from about 1 to about 5.

Further, the present invention surfactant composition may comprise amixture of branched primary alkyl alkoxylated sulfates having theformula ##STR28## wherein the total number of carbon atoms per molecule,including branching, is from 14 to 20, and wherein further for thissurfactant mixture the average total number of carbon atoms in thebranched primary alkyl moieties having the above formula is within therange of greater than 14.5 to about 17.5; R, R¹, and R² are eachindependently selected from hydrogen and C₁ -C₃ alkyl, provided R, R¹,and R² are not all hydrogen; M is a water soluble cation; w is aninteger from 0 to 13; x is an integer from 0 to 13; y is an integer from0 to 13; z is an integer of at least 1; w+x+y+z is from 8 to 14; EO/POare alkoxy moieties, preferably selected from ethoxy, propoxy, and mixedethoxy/propoxy groups, wherein m is at least about 0.01, preferablywithin the range of from about 0.1 to about 30, more preferably fromabout 0.5 to about 10, and most preferably from about 1 to about 5;provided that when R² is C₁ -C₃ alkyl the ratio of surfactants having zequal to 2 or greater to surfactants having z of 1 is at least about1:1, preferably at least about 1.5:1, more preferably at least about3:1, and most preferably at least about 4:1. Also preferred aresurfactant compositions when R² is C₁ -C₃ alkyl comprising less thanabout 50%, preferably less than about 40%, more preferably less thanabout 25%, most preferably less than about 20%, of branched primaryalkyl alkoxylated sulfate having the above formula wherein z equals 1.

Preferred mono-methyl branched primary alkyl ethoxylated sulfates areselected from the group consisting of 3-methyl pentadecanol ethoxylatedsulfate, 4-methyl pentadecanol ethoxylated sulfate, 5-methylpentadecanol ethoxylated sulfate, 6-methyl pentadecanol ethoxylatedsulfate, 7-methyl pentadecanol ethoxylated sulfate, 8-methylpentadecanol ethoxylated sulfate, 9-methyl pentadecanol ethoxylatedsulfate, 10-methyl pentadecanol ethoxylated sulfate, 11-methylpentadecanol ethoxylated sulfate, 12-methyl pentadecanol ethoxylatedsulfate, 13-methyl pentadecanol ethoxylated sulfate, 3-methylhexadecanol ethoxylated sulfate, 4-methyl hexadecanol ethoxylatedsulfate, 5-methyl hexadecanol ethoxylated sulfate, 6-methyl hexadecanolethoxylated sulfate, 7-methyl hexadecanol ethoxylated sulfate, 8-methylhexadecanol ethoxylated sulfate, 9-methyl hexadecanol ethoxylatedsulfate, 10-methyl hexadecanol ethoxylated sulfate, 11-methylhexadecanol ethoxylated sulfate, 12-methyl hexadecanol ethoxylatedsulfate, 13-methyl hexadecanol ethoxylated sulfate, 14-methylhexadecanol ethoxylated sulfate, and mixtures thereof, wherein thecompounds are ethoxylated with an average degree of ethoxylation of fromabout 0.1 to about 10.

Preferred di-methyl branched primary alkyl ethoxylated sulfates selectedfrom the group consisting of: 2,3-methyl tetradecanol ethoxylatedsulfate, 2,4-methyl tetradecanol ethoxylated sulfate, 2,5-methyltetradecanol ethoxylated sulfate, 2,6-methyl tetradecanol ethoxylatedsulfate, 2,7-methyl tetradecanol ethoxylated sulfate, 2,8-methyltetradecanol ethoxylated sulfate, 2,9-methyl tetradecanol ethoxylatedsulfate, 2,10-methyl tetradecanol ethoxylated sulfate, 2,11-methyltetradecanol ethoxylated sulfate, 2,12-methyl tetradecanol ethoxylatedsulfate, 2,3-methyl pentadecanol ethoxylated sulfate, 2,4-methylpentadecanol ethoxylated sulfate, 2,5-methyl pentadecanol ethoxylatedsulfate, 2,6-methyl pentadecanol ethoxylated sulfate, 2,7-methylpentadecanol ethoxylated sulfate, 2,8-methyl pentadecanol ethoxylatedsulfate, 2,9-methyl pentadecanol ethoxylated sulfate, 2,10-methylpentadecanol ethoxylated sulfate, 2,11-methyl pentadecanol ethoxylatedsulfate, 2,12-methyl pentadecanol ethoxylated sulfate, 2,13-methylpentadecanol ethoxylated sulfate, and mixtures thereof, wherein thecompounds are ethoxylated with an average degree of ethoxylation of fromabout 0.1 to about 10.

Preparation of Mid-chain Branched Surfactants

The following reaction scheme outlines a general approach to thepreparation of the mid-chain branched primary alcohol useful foralkoxylating and/or sulfating to prepare the mid-chain branched primaryalkyl surfactants of the present invention. ##STR29##

An alkyl halide is converted to a Grignard reagent and the Grignard isreacted with a haloketone. After conventional acid hydrolysis,acetylation and thermal elimination of acetic acid, an intermediateolefin is produced (not shown in the scheme) which is hydrogenatedforthwith using any convenient hydrogenation catalyst such as Pd/C.

This route is favorable over others in that the branch, in thisillustration a 5-methyl branch, is introduced early in the reactionsequence.

Formylation of the alkyl halide resulting from the first hydrogenationstep yields alcohol product, as shown in the scheme. This can bealkoxylated using standard techniques and/or sulfated using anyconvenient sulfating agent, e.g., chlorosulfonic acid, SO3/air, oroleum, to yield the final branched primary alkyl surfactant. There isflexibility to extend the branching one additional carbon beyond thatwhich is achieved by a single formylation. Such extension can, forexample, be accomplished by reaction with ethylene oxide. See "GrignardReactions of Nonmetallic Substances", M. S. Kharasch and O. Reinmuth,Prentice-Hall, N.Y., 1954; J. Org. Chem., J. Cason and W. R. Winans,Vol. 15 (1950), pp 139-147; J. Org Chem., J. Cason et al., Vol. 13(1948), pp 239-248; J Org Chem., J. Cason et al., Vol. 14 (1949), pp147-154; and J. Org Chem., J. Cason et al., Vol. 15 (1950), pp 135-138all of which are incorporated herein by reference.

In variations of the above procedure, alternate haloketones or Grignardreagents may be used. PBr3 halogenation of the alcohol from formylationor ethoxylation can be used to accomplish an iterative chain extension.

The preferred mid-chained branched primary alkyl alkoxylated sulfates(as well as the polyoxyalkylenes and alkyl sulfates, by choosing to onlyalkoxylate or sulfate the intermediate alcohol produced) of the presentinvention can also be readily prepared as follows: ##STR30##

A conventional bromoalcohol is reacted with triphenylphosphine followedby sodium hydride, suitably in dimethylsulfoxide/tetrahydrofuran, toform a Wittig adduct. The Wittig adduct is reacted with an alpha methylketone, forming an internally unsaturated methyl-branched alcoholate.Hydrogenation followed by alkoxylation and/or sulfation yields thedesired mid-chain branched primary alkyl surfactant. Although the Wittigapproach does not allow the practitioner to extend the hydrocarbonchain, as in the Grignard sequence, the Wittig typically affords higheryields. See Agricultural and Biological Chemistry, M. Horiike et al.,vol. 42 (1978), pp 1963-1965 included herein by reference.

Any alternative synthetic procedure in accordance with the invention maybe used to prepare the branched primary alkyl surfactants. The mid-chainbranched primary alkyl surfactants may, in addition be synthesized orformulated in the presence of the conventional homologs, for example anyof those which may be formed in an industrial process which produces2-alkyl branching as a result of hydroformylation. Mid-chain branchedsurfactant mixtures of the present invention are routinely added toother known commercial alkyl surfactants contained in the final laundryproduct formulation.

In certain preferred embodiments of the surfactant mixtures of thepresent invention, especially those derived from fossil fuel sourcesinvolving commercial processes, comprise at least 1 mid-chain branchedprimary alkyl surfactant, preferably at least 2, more preferably atleast 5, most preferably at least 8.

Particularly suitable for preparation of certain surfactant mixtures ofthe present invention are "oxo" reactions wherein a branched chainolefin is subjected to catalytic isomerization and hydroformylationprior to alkoxylation and/or sulfation. The preferred processesresulting in such mixtures utilize fossil fuels as the starting materialfeedstock. Preferred processes utilize Oxo reaction on linear olefins(alpha or internal) with a limited amount of branching. Suitable olefinsmay be made by dimerization of linear alpha or internal olefins, bycontrolled oligomerization of low molecular weight linear olefins, byskeletal rearrangement of detergent range olefins, bydehydrogenation/skeletal rearrangement of detergent range paraffins, orby Fischer-Tropsch reaction. These reactions will in general becontrolled to:

1) give a large proportion of olefins in the desired detergent range(while allowing for the addition of a carbon atom in the subsequent Oxoreaction),

2) produce a limited number of branches, preferably mid-chain,

3) produce C₁ -C₃ branches, more preferably ethyl, most preferablymethyl,

4) limit or eliminate gem dialkyl branching i.e. to avoid formation ofquaternary carbon atoms. The suitable olefins can undergo Oxo reactionto give primary alcohols either directly or indirectly through thecorresponding aldehydes. When an internal olefin is used, an Oxocatalyst is normally used which is capable of prior pre-isomerization ofinternal olefins primarily to alpha olefins. While a separatelycatalyzed (i.e. non-Oxo) internal to alpha isomerization could beeffected, this is optional. On the other hand, if the olefin-formingstep itself results directly in an alpha olefin (e.g. with high pressureFischer-Tropsch olefins of detergent range), then use of anon-isomerizing Oxo catalyst is not only possible, but preferred.

The process described herein above gives the more preferred5-methyl-hexadecyl surfactants in higher yield than the less preferred2,4-dimethylpentadecyl surfactants. This mixture is desirable under themetes and bounds of the present invention in that each product comprisesat total of 17 carbon atoms with linear alkyl chains having at least 13carbon atoms.

The following examples provide methods for synthesizing variouscompounds useful in the present invention compositions.

EXAMPLE I Preparation of Sodium 7-methylhexadecyl Ethoxylate (E2) andEthoxylated Sulfate Synthesis of (6-hydroxyhexyl) TriphenylphosphoniumBromide

Into a 5 L, 3 neck round bottom flask fitted with nitrogen inlet,condenser, thermometer, mechanical stirring and nitrogen outlet is added6-bromo-1-hexanol (500 g, 2.76 mol), triphenylphosphine (768 g, 2.9 mol)and acetonitrile (1800 ml) under nitrogen. The reaction mixture isheated to reflux for 72 hrs. The reaction mixture is cooled to roomtemperature and transferred into a 5 L beaker. The product isrecrystallized from anhydrous ethyl ether (1.5 L) at 10° C. Vacuumfiltration followed by washing with ethyl ether and drying in a vacuumoven at 50° C. for 2 hrs. gives 1140 g of the desired product as whitecrystals.

Synthesis of 7-methylhexadecene-1-ol

Into a dried 5 L, 3 neck round bottom flask fitted with mechanicalstirring, nitrogen inlet, dropping funnel, thermometer and nitrogenoutlet is added 70.2 g of 60% sodium hydride (1.76 mol) in mineral oil.The mineral oil is removed by washing with hexanes. Anhydrous dimethylsulfoxide (500 ml) is added to the flask and the mixture is heated to70° C. until evolution of hydrogen stops. The reaction mixture is cooledto room temperature followed by addition of 1 L of anhydroustetrahydrofuran. (6-hydroxyhexyl) triphenylphosphonium bromide (443.4 g,1 mol) is slurried with warm anhydrous dimethyl sulfoxide (50° C., 500ml) and slowly added to the reaction mixture through the dropping funnelwhile keeping it at 25-30° C. The mixture is stirred for 30 minutes atroom temperature at which time 2-undecanone (187 g, 1.1 mol) is slowlyadded through a dropping funnel. Reaction is slightly exothermic andcooling is needed to maintain 25-30° C. The mixture is stirred for 18hr. and then poured into a 5 L beaker containing 1 L purified water withstirring. The oil phase (top) is allowed to separate out in a separatoryfunnel and the water phase is removed. The water phase is washed withhexanes (500 ml) and the organic phase is separated and combined withthe oil phase from the water wash. The organic mixture is then extractedwith water 3 times (500 ml each) followed by vacuum distillation tocollect the clear, oily product (132 g) at 140C and 1 mm Hg.

Hydrogenation of 7-methylhexadecene-1-ol

Into a 3 L rocking autoclave liner is added 7-methylhexadecene-1-ol (130g, 0.508 mol), methanol (300 ml) and platinum on carbon (10% by weight,35 g). The mixture is hydrogenated at 180° C. under 1200 psig ofhydrogen for 13 hrs., cooled and vacuum filtered thru Celite 545 withwashing of the Celite 545, suitably with methylene chloride. If needed,the filtration can be repeated to eliminate traces of Pt catalyst, andmagnesium sulfate can be used to dry the product. The solution ofproduct is concentrated on a rotary evaporator to obtain a clear oil(124 g).

Alkoxylation of 7-methylhexadecanol

Into a dried 1 L 3 neck round bottom flask fitted with a nitrogen inlet,mechanical stirrer, and a y-tube fitted with a thermometer and a gasoutlet is added the alcohol from the preceeding step. For purposes ofremoving trace amounts of moisture, the alcohol is sparged with nitrogenfor about 30 minutes at 80-100° C. Continuing with a nitrogen sweep,sodium metal is added as the catalyst and allowed to melt with stirringat 120-140° C. With vigorous stirring, ethylene oxide gas is added in140 minutes while keeping the reaction temperature at 120-140° C. Afterthe correct weight (equal to two equivalents of ethylene oxide) has beenadded, nitrogen is swept through the apparatus for 20-30 minutes as thesample is allowed to cool. The desired 7-methylhexadecyl ethoxylate(average of 2 ethoxylates per molecule) product is then collected.

Sulfation of 7-methylhexadecyl Ethoxylate (E2)

Into a dried 1 L 3 neck round bottom flask fitted with a nitrogen inlet,dropping funnel, thermometer, mechanical stirring and nitrogen outlet isadded chloroform and 7-methylhexadecyl ethoxylate (E2) from thepreceeding step. Chlorosulfonic acid is slowly added to the stirredmixture while maintaining 25-30° C. temperature with an ice bath. OnceHCl evolution has stopped slowly add sodium methoxide (25% in methanol)while keeping temperature at 25-30° C. until a aliquot at 5%concentration in water maintains a pH of 10.5. To the mixture is addedhot ethanol (55° C.) and vacuum filtered immediately. The filtrate isconcentrated to a slurry on a rotary evaporator, cooled and then pouredinto ethyl ether. The mixture is chilled to 50° C. and vacuum filteredto provide the desired 7-methylhexadecyl ethoxylate (average of 2ethoxylates per molecule) sulfate, sodium salt, product.

EXAMPLE II Synthesis of Sodium 7-methylpentadecyl Ethoxylate (E5) andEthoxylated Sulfate Synthesis of (6-hydroxyhexyl) TriphenylphosphoniumBromide

Into a 5 L, 3 neck round bottom flask fitted with nitrogen inlet,condenser, thermometer, mechanical stirring and nitrogen outlet is added6-bromo-1-hexanol (500 g, 2.76 mol), triphenylphosphine (768 g, 2.9 mol)and acetonitrile (1800 ml) under nitrogen. The reaction mixture isheated to reflux for 72 hrs. The reaction mixture is cooled to roomtemperature and transferred into a 5 L beaker. The product isrecrystallized from anhydrous ethyl ether (1.5 L) at 10° C. Vacuumfiltration of the mixture followed by washing the white crystals withethyl ether and drying in a vacuum oven at 50° C. for 2 hrs. gives 1140g of the desired product.

Synthesis of 7-methylpentadecene-1-ol

Into a dried 5 L, 3 neck round bottom flask fitted with mechanicalstirring, nitrogen inlet, dropping funnel, thermometer and nitrogenoutlet is added 80 g of 60% sodium hydride (2.0 mol) in mineral oil. Themineral oil is removed by washing with hexanes. Anhydrous dimethylsulfoxide (500 ml) is added to the flask and heated to 70° C. untilevolution of hydrogen stops. The reaction mixture is cooled to roomtemperature followed by addition of 1 L of anhydrous tetrahydrofuran.(6-hydroxyhexyl) triphenylphosphonium bromide (443.4 g, 1 mol) isslurried with warm anhydrous dimethyl sulfoxide (50° C., 500 ml) andslowly added to the reaction mixture thru the dropping funnel whilekeeping the reaction at 25-30° C. The reaction is stirred for 30 minutesat room temperature at which time 2-decanone (171.9 g, 1.1 mol) isslowly added thru a dropping funnel. Reaction is slightly exothermic andcooling is needed to maintain 25-30° C. Mixture is stirred for 18 hrs.and then poured into a separatory funnel containing 600 ml of purifiedwater and 300 ml of hexanes. After shaking the oil phase (top) isallowed to separate out and the water phase is removed. The extractionsof the oil phase are continued using water until both phases are clear.The organic phase is collected, vacuum distilled and purified by liquidchromatography (90:10 hexanes:ethyl acetate, silica gel stationaryphase) to obtain a clear, oily product (119.1 g).

Hydrogenation of 7-methylpentadecene-1-ol

Into a 3 L rocking autoclave glass liner (Autoclave Engineers) is added7-Methylpentadecene-1-ol (122 g, 0.508 mol), methanol (300 ml) andplatinum on carbon (10% by weight, 40 g). The mixture is hydrogenated at180° C. under 1200 psig of hydrogen for 13 hrs., cooled and vacuumfiltered thru Celite 545 with washing of Celite 545 with methylenechloride. The organic mixture is still dark from platinum catalyst sothe filtration procedure is repeated with concentration on a rotaryevaporator, dilution is carried out with methylene chloride (500 ml) andmagnesium sulfate is added to dry product. Vacuum filter thru Celite 545and concentrate filtrate on a rotary evaporator to obtain a clear oil(119 g).

Alkoxylation of 7-methylpentadecanol

Into a dried 1 L 3 neck round bottom flask fitted with a nitrogen inlet,mechanical stirrer, and a y-tube fitted with a thermometer and a gasoutlet is added the alcohol from the preceeding step. For purposes ofremoving trace amounts of moisture, the alcohol is sparged with nitrogenfor about 30 minutes at 80-100° C. Continuing with a nitrogen sweep,sodium metal is added as the catalyst and allowed to melt with stirringat 120-140° C. With vigorous stirring, ethylene oxide gas is added in140 minutes while keeping the reaction temperature at 120-140° C. Afterthe correct weight (equal to five equivalents of ethylene oxide) hasbeen added, nitrogen is swept through the apparatus for 20-30 minutes asthe sample is allowed to cool. The desired 7-methylpentadecyl ethoxylate(average of 5 ethoxylates per molecule) product is then collected.

Sulfation of 7-methylpentadecyl Ethoxylate (E5)

Into a dried 1 L 3 neck round bottom flask fitted with a nitrogen inlet,dropping funnel, thermometer, mechanical stirring and nitrogen outlet isadded chloroform and 7-methylpentadecyl ethoxylate (E5) from thepreceeding step. Chlorosulfonic acid is slowly added to the stirredmixture while maintaining 25-30° C. temperature with a ice bath. OnceHCl evolution has stopped slowly add sodium methoxide (25% in methanol)while keeping temperature at 25-30° C. until a aliquot at 5%concentration in water maintains a pH of 10.5. To the mixture is addedmethanol and 1-butanol. Vacuum filter off the inorganic salt precipitateand remove methanol from the filtrate on a rotary evaporator. Cool toroom temperature, add ethyl ether and let stand for 1 hour. Theprecipitate is collected by vacuum filtration to provide the desired7-methylpentadecyl ethoxylate (average of 5 ethoxylates per molecule)sulfate, sodium salt, product.

EXAMPLE III Synthesis of Sodium 7-methylheptadecyl Ethoxylated (E1.5)and Sulfate Synthesis of (6-Hydroxyhexyl) Triphenylphosphonium Bromide

Into a 5 L, 3 neck round bottom flask fitted with nitrogen inlet,condenser, thermometer, mechanical stirring and nitrogen outlet is added6-bromo-1-hexanol (500 g, 2.76 mol), triphenylphosphine (768 g, 2.9 mol)and acetonitrile (1800 ml) under nitrogen. The reaction mixture isheated to reflux for 72 hrs. The reaction mixture is cooled to roomtemperature and transferred into a 5 L beaker. The product isrecrystallized from anhydrous ethyl ether (1.5L) at 10° C. Vacuumfiltration of the mixture followed by washing the white crystals withethyl ether and drying in a vacuum oven at 50° C. for 2 hrs. gives 1140g of the desired product.

Synthesis of 7-methylheptadecene-1-ol

Into a dried 5 L, 3 neck round bottom flask fitted with mechanicalstirring, nitrogen inlet, dropping funnel, thermometer and nitrogenoutlet is added 80 g of 60% sodium hydride (2.0 mol) in mineral oil. Themineral oil is removed by washing with hexanes. Anhydrous dimethylsulfoxide (500 ml) is added to the flask and heated to 70° C. untilevolution of hydrogen stops. The reaction mixture is cooled to roomtemperature followed by addition of 1 L of anhydrous tetrahydrofuran.(6-hydroxyhexyl) triphenylphosphonium bromide (443.4 g, 1 mol) isslurried with warm anhydrous dimethyl sulfoxide (50° C., 500 ml) andslowly added to the reaction mixture thru the dropping funnel whilekeeping the reaction at 25-30° C. The reaction is stirred for 30 minutesat room temperature at which time 2-dodecanone (184.3 g, 1.1 mol) isslowly added thru a dropping funnel. Reaction is slightly exothermic andcooling is needed to maintain 25-30° C. Mixture is stirred for 18 hrs.and then poured into a separatory funnel containing 600 ml of purifiedwater and 300 ml of hexanes. After shaking the oil phase (top) isallowed to separate out and the water phase is removed which is cloudy.The extractions are continued using water until the water phase and theorganic phase become clear. The organic phase is collected and purifiedby liquid chromatography (mobile phase-hexanes, stationary phase-silicagel) to obtain a clear, oily product (116 g). HNMR of the final product(in deuterium oxide) indicates a CH₂ --OSO₃ -- triplet at the 3.8 ppmresonance, CH₂ --CH₂ --OSO₃ -- multiplet at the 1.5 ppm resonance, CH₂of the alkyl chain at the 0.9-1.3 ppm resonance and CH--CH₃ branch pointoverlapping the R--CH₂ CH₃ terminal methyl group at the 0.8 ppmresonance.

Hydrogenation of 7-methylheptadecene-1-ol

Into a 3 L rocking autoclave glass liner (Autoclave Engineers) is added7-Methylheptadecene-1-ol (116 g, 0.433 mol), methanol (300 ml) andplatinum on carbon (10% by weight, 40 g). The mixture is hydrogenated at180° C. under 1200 psig of hydrogen for 13 hrs., cooled and vacuumfiltered thru Celite 545 with washing of Celite 545 with methylenechloride. Vacuum filter thru Celite 545 and concentrate filtrate on arotary evaporator to obtain a clear oil (108 g).

Alkoxylation of 7-methylpentadecanol

Into a dried 1 L 3 neck round bottom flask fitted with a nitrogen inlet,mechanical stirrer, and a y-tube fitted with a thermometer and a gasoutlet is added the alcohol from the preceeding step. For purposes ofremoving trace amounts of moisture, the alcohol is sparged with nitrogenfor about 30 minutes at 80-100° C. Continuing with a nitrogen sweep,sodium metal is added as the catalyst and allowed to melt with stirringat 120-140° C. With vigorous stirring, ethylene oxide gas is added in140 minutes while keeping the reaction temperature at 120-140° C. Afterthe correct weight (equal to 1.5 equivalents of ethylene oxide) has beenadded, nitrogen is swept through the apparatus for 20-30 minutes as thesample is allowed to cool. The desired 7-methylheptadecyl ethoxylate(average of 1.5 ethoxylates per molecule) product is then collected.

Sulfation of 7-methylheptadecyl Ethoxylate (E1.5)

Into a dried 1 L 3 neck round bottom flask fitted with a nitrogen inlet,dropping funnel, thermometer, mechanical stirring and nitrogen outlet isadded chloroform and 7-methylheptadecyl ethoxylate (E1.5) from thepreceeding step. Chlorosulfonic acid is slowly added to the stirredmixture while maintaining 25-30° C. temperature with a ice bath. OnceHCl evolution has stopped slowly add sodium methoxide (25% in methanol)while keeping temperature at 25-30° C. until a aliquot at 5%concentration in water maintains a pH of 10.5. To the mixture is addedhot methanol (45° C.) to dissolve the branched sulfate followedimmediately by vacuum filtration to remove the inorganic saltprecipitate and repeated a second time. The filtrate is then cooled to5° C. at which time ethyl ether is added and let stand for 1 hour. Theprecipitate is collected by vacuum filtration to provide the desired7-methylheptadecyl ethoxylate (average of 1.5 ethoxylates per molecule)sulfate, sodium salt, product.

EXAMPLE IV

The following Shell Research experimental test alcohol samples areethoxylated (average ethoxylation of 2.5) and then sulfated by thefollowing procedure.

    ______________________________________                                        .sup.13 C-NMR Results For Branched Alcohols Prepared                              Total Number of Carbons                                                                           16       17   18                                      ______________________________________                                        Avg. Number of Branches per                                                                       2.0      1.7    2.1                                         Molecule                                                                      Average Branch Position Relative To                                           Hydroxyl Carbon                                                               % at C4 and higher 56% 55% 52%                                                % at C3 26% 21% 25%                                                           % at C2 18% 24% 23%                                                           Type of Branching                                                             % propyl and higher 31% 35% 30%                                               % ethyl 12% 10% 12%                                                           % methyl 57% 55% 58%                                                        ______________________________________                                    

Into a dried 250 ml 3 neck round bottom flask fitted with a nitrogeninlet, mechanical stirrer, and a y-tube fitted with a thermometer and agas outlet is added the C16 alcohol (48.4 g, 0.2 mol) above. Forpurposes of removing trace amounts of moisture, the alcohol is spargedwith nitrogen for about 30 minutes at 80-100° C. Continuing with anitrogen sweep, sodium metal (0.23 g, 0.01 mol) is added as the catalystand allowed to melt with stirring at 120-140° C. With vigorous stirring,ethylene oxide gas (22 g, 0.5 mol) is added in 140 minutes while keepingthe reaction temperature at 120-140° C. After the correct weight ofethylene oxide (average 2.5 ethoxylates per molecule) has been added,nitrogen is swept through the apparatus for 20-30 minutes as the sampleis allowed to cool. The gold liquid product (69 g, 0.196 mol) is bottledunder nitrogen.

Sulfation of this C16 ethoxylate utilizes the following procedure. Intoa dried 500 ml 3 neckround bottom flask fitted with a gas inlet,dropping funnel, mechanical stirrer, and a y-tube fitted with athermometer and a gas outlet is added the C16 ethoxylate from theprevious step (63.4 g, 0.18 mol) and diethyl ether (75 ml).Chlorosulfonic acid (22.1 g, 0.19 mol) is added slowly to the stirredmixture while maintaining a reaction temperature of 5-15° C. with an icewater bath. After the chlorosulfonic acid is added a slow nitrogen sweepand a vacuum (10-15 inches Hg) is begun to remove HCl. Also the reactionis warmed to 30-40° C. with the addition of a warm water bath. Afterabout 45 minutes the vacuum is increased to 25-30 inches Hg andmaintained for an additional 45 minutes. The acidic reaction mixture isslowly poured into a vigorously stirred beaker of 25% sodium methoxide(43.2 g, 0.2 mol) and methanol (200 ml) that is cooled in an ice waterbath. After pH<12 is confirmed the solution is allowed to stir about 15minutes then poured into a glass dish. Most of the solvent is allowed toevaporate overnight in the fume hood. The next morning the dish istransferred to a vacuum drying oven. The sample is allowed to dry allday and overnight at 40-60° C. with 25-30 inches Hg vacuum. Yellow tackysolid (80.9 g; 93% active) C16 ethoxylated (E2.5) sulfate, sodium salt,product is collected.

EXAMPLE V Preparation of Sodium 7-methylhexadecyl Sulfate Sulfation of7-methylhexadecanol

Into a dried 1 L 3 neck round bottom flask fitted with a nitrogen inlet,dropping funnel, thermometer, mechanical stirring and nitrogen outlet isadded chloroform (300 ml) and 7-methylhexadecanol (124 g, 0.484 mol),prepared as an intermediate in Example I. Chlorosulfonic acid (60 g,0.509 mol) is slowly added to the stirred mixture while maintaining25-30° C. temperature with a ice bath. Once HCl evolution has stopped (1hr.) slowly add sodium methoxide (25% in methanol) while keepingtemperature at 25-30° C. until an aliquot at 5% concentration in watermaintains a pH of 10.5. To the mixture is added hot ethanol (55° C., 2L). The mixture is vacuum filtered immediately. The filtrate isconcentrated to a slurry on a rotary evaporator, cooled and then pouredinto 2 L of ethyl ether. The mixture is chilled to 5° C., at which pointcrystallization occurs, and vacuum filtered. The crystals are dried in avacuum oven at 50C for 3 hrs. to obtain a white solid (136 g, 92% activeby cat SO₃ titration).

EXAMPLE VI Synthesis of Sodium 7-methylpentadecyl Sulfate Sulfation of7-methylpentadecanol

Into a dried 1 L 3 neck round bottom flask fitted with a nitrogen inlet,dropping funnel, thermometer, mechanical stirring and nitrogen outlet isadded chloroform (300 ml) and 7-methylpentadecanol (119 g, 0.496 mol),prepared as an intermediate in Example II. Chlorosulfonic acid (61.3 g,0.52 mol) is slowly added to the stirred mixture while maintaining25-30° C. temperature with an ice bath. Once HCl evolution has stopped(1 hr.) slowly add sodium methoxide (25% in methanol) while keepingtemperature at 25-30° C. until a aliquot at 5% concentration in watermaintains a pH of 10.5. To the mixture is added methanol (1 L) and 300ml of 1-butanol. Vacuum filter off the inorganic salt precipitate andremove methanol from the filtrate on a rotary evaporator. Cool to roomtemperature, add 1 L of ethyl ether and let stand for 1 hour. Theprecipitate is collected by vacuum filtration. The product is dried in avacuum oven at 50C for 3 hrs. to obtain a white solid (82 g, 90% activeby cat SO₃ titration).

EXAMPLE VII Synthesis of Sodium 7-methylheptadecyl Sulfate Sulfation of7-methylheptadecanol

Into a dried 1 L 3 neck round bottom flask fitted with a nitrogen inlet,dropping funnel, thermometer, mechanical stirring and nitrogen outlet isadded chloroform (300 ml) and 7-Methylheptadecanol (102 g, 0.378 mol),prepared as an intermediate in Example III. Chlorosulfonic acid (46.7 g,0.40 mol) is slowly added to the stirred mixture while maintaining25-30° C. temperature with a ice bath. Once HCl evolution has stopped (1hr.) slowly add sodium methoxide (25% in methanol) while keepingtemperature at 25-30° C. until an aliquot at 5% concentration in watermaintains a pH of 10.5. To the mixture is added hot methanol (45° C., 1L) to dissolve the branched sulfate followed immediately by vacuumfiltration to remove the inorganic salt precipitate and repeated asecond time. The filtrate is then cooled to 5° C. at which time 1 L ofethyl ether is added and let stand for 1 hour. The precipitate iscollected by vacuum filtration. The product is dried in a vacuum oven at50C. for 3 hrs. to obtain a white solid (89 g, 88% active by cat SO₃titration). HNMR of the final product (in deuterium oxide) indicates aCH₂ --OSO₃ -- triplet at the 3.8 ppm resonance, CH₂ --CH₂ --OSO₃ --multiplet at the 1.5 ppm resonance, CH₂ of the alkyl chain at the0.9-1.3 ppm resonance and CH--CH₃ branch point overlapping the R--CH₂CH₃ terminal methyl group at the 0.8 ppm resonance. Mass spectrometrydata shows a molecular ion peak with a mass of 349.1 corresponding tothe 7-methylheptadecyl sulfate ion. Also shown is the methyl branch atthe 7 position due to the loss of 29 mass units at that position.

The following two analytical methods for characterizing branching in thepresent invention surfactant compositions are useful:

1) Separation and Identification of Components in Fatty Alcohols (priorto alkoxylation or after hydrolysis of alcohol sulfate for analyticalpurposes). The position and length of branching found in the precursorfatty alcohol materials is determined by GC/MS techniques [see: D. J.Harvey, Biomed, Environ. Mass Spectrom (1989). 18(9), 719-23; D. J.Harvey, J. M. Tiffany, J. Chromatogr. (1984), 301(1), 173-87; K. A.Karlsson, B. E. Samuelsson, G. O. Steen, Chem. Phys. Lipids (1973),11(1), 17-38].

2) Identification of Separated Fatty Alcohol Alkoxy Sulfate Componentsby MS/MS. The position and length of branching is also determinable byIon Spray-MS/MS or FAB-MS/MS techniques on previously isolated fattyalcohol sulfate components.

The average total carbon atoms of the branched primary alkyl surfactantsherein can be calculated from the hydroxyl value of the precursor fattyalcohol mix or from the hydroxyl value of the alcohols recovered byextraction after hydrolysis of the alcohol sulfate mix according tocommon procedures, such as outlined in "Bailey's Industrial Oil and FatProducts", Volume 2, Fourth Edition, edited by Daniel Swern, pp.440-441.

Bleaching Compounds--Bleaching Agents and Bleach Activators--Thedetergent compositions herein preferably further contain bleachingagents or bleaching compositions containing a bleaching agent and one ormore bleach activators. Bleaching agents will typically be at levels offrom about 1% to about 30%, more typically from about 5% to about 20%,of the detergent composition, especially for fabric laundering. Ifpresent, the amount of bleach activators will typically be from about0.1% to about 60%, more typically from about 0.5% to about 40% of thebleaching composition comprising the bleaching agent-plus-bleachactivator.

The bleaching agents used herein can be any of the bleaching agentsuseful for detergent compositions in textile cleaning, hard surfacecleaning, or other cleaning purposes that are now known or become known.These include oxygen bleaches as well as other bleaching agents.Perborate bleaches, e.g., sodium perborate (e.g., mono-or tetra-hydrate)can be used herein.

Another category of bleaching agent that can be used without restrictionencompasses percarboxylic acid bleaching agents and salts thereof.Suitable examples of this class of agents include magnesiummonoperoxyphthalate hexahydrate, the magnesium salt of metachloroperbenzoic acid, 4-nonylamino-4-oxoperoxybutyric acid anddiperoxydodecanedioic acid. Such bleaching agents are disclosed in U.S.Pat. No. 4,483,781, Hartman, issued Nov. 20, 1984, U.S. patentapplication Ser. No. 740,446, Burns et al, filed Jun. 3, 1985, EuropeanPatent Application 0,133,354, Banks et al, published Feb. 20, 1985, andU.S. Pat. No. 4,412,934, Chung et al, issued Nov. 1, 1983. Highlypreferred bleaching agents also include 6-nonylamino-6-oxoperoxycaproicacid as described in U.S. Pat. No. 4,634,551, issued Jan. 6, 1987 toBurns et al.

Peroxygen bleaching agents can also be used. Suitable peroxygenbleaching compounds include sodium carbonate peroxyhydrate andequivalent "percarbonate" bleaches, sodium pyrophosphate peroxyhydrate,urea peroxyhydrate, and sodium peroxide. Persulfate bleach (e.g., OXONE,manufactured commercially by DuPont) can also be used.

A preferred percarbonate bleach comprises dry particles having anaverage particle size in the range from about 500 micrometers to about1,000 micrometers, not more than about 10% by weight of said particlesbeing smaller than about 200 micrometers and not more than about 10% byweight of said particles being larger than about 1,250 micrometers.Optionally, the percarbonate can be coated with silicate, borate orwater-soluble surfactants. Percarbonate is available from variouscommercial sources such as FMC, Solvay and Tokai Denka.

Mixtures of bleaching agents can also be used.

Peroxygen bleaching agents, the perborates, the percarbonates, etc., arepreferably combined with bleach activators, which lead to the in situproduction in aqueous solution (i.e., during the washing process) of theperoxy acid corresponding to the bleach activator. Various nonlimitingexamples of activators are disclosed in U.S. Pat. No. 4,915,854, issuedApr. 10, 1990 to Mao et al, and U.S. Pat. No. 4,412,934. Thenonanoyloxybenzene sulfonate (NOBS) and tetraacetyl ethylene diamine(TAED) activators are typical, and mixtures thereof can also be used.See also U.S. Pat. No. 4,634,551 for other typical bleaches andactivators useful herein.

Highly preferred amido-derived bleach activators are those of theformulae:

    R.sup.1 N(R.sup.5)C(O)R.sup.2 C(O)L or R.sup.1 C(O)N(R.sup.5)R.sup.2 C(O)L

wherein R¹ is an alkyl group containing from about 6 to about 12 carbonatoms, R² is an alkylene containing from 1 to about 6 carbon atoms, R⁵is H or alkyl, aryl, or alkaryl containing from about 1 to about 10carbon atoms, and L is any suitable leaving group. A leaving group isany group that is displaced from the bleach activator as a consequenceof the nucleophilic attack on the bleach activator by the perhydrolysisanion. A preferred leaving group is phenyl sulfonate.

Preferred examples of bleach activators of the above formulae include(6-octanamido-caproyl)oxybenzenesulfonate,(6-nonanamidocaproyl)oxybenzenesulfonate,(6-decanamido-caproyl)oxybenzenesulfonate, and mixtures thereof asdescribed in U.S. Pat. No. 4,634,551, incorporated herein by reference.

Another class of bleach activators comprises the benzoxazin-typeactivators disclosed by Hodge et al in U.S. Pat. No. 4,966,723, issuedOct. 30, 1990, incorporated herein by reference. A highly preferredactivator of the benzoxazin-type is: ##STR31##

Still another class of preferred bleach activators includes the acyllactam activators, especially acyl caprolactams and acyl valerolactamsof the formulae: ##STR32## wherein R⁶ is H or an alkyl, aryl,alkoxyaryl, or alkaryl group containing from 1 to about 12 carbon atoms.Highly preferred lactam activators include benzoyl caprolactam, octanoylcaprolactam, 3,5,5-trimethylhexanoyl caprolactam, nonanoyl caprolactam,decanoyl caprolactam, undecenoyl caprolactam, benzoyl valerolactam,octanoyl valerolactam, decanoyl valerolactam, undecenoyl valerolactam,nonanoyl valerolactam, 3,5,5-trimethylhexanoyl valerolactam and mixturesthereof See also U.S. Pat. No. 4,545,784, issued to Sanderson, Oct. 8,1985, incorporated herein by reference, which discloses acylcaprolactams, including benzoyl caprolactam, adsorbed into sodiumperborate.

Bleaching agents other than oxygen bleaching agents are also known inthe art and can be utilized herein. One type of non-oxygen bleachingagent of particular interest includes photoactivated bleaching agentssuch as the sulfonated zinc and/or aluminum phthalocyanines. See U.S.Pat. No. 4,033,718, issued Jul. 5, 1977 to Holcombe et al. If used,detergent compositions will typically contain from about 0.025% to about1.25%, by weight, of such bleaches, especially sulfonate zincphthalocyanine.

If desired, the bleaching compounds can be catalyzed by means of amanganese compound. Such compounds are well known in the art andinclude, for example, the manganese-based catalysts disclosed in U.S.Pat. No. 5,246,621, U.S. Pat. No. 5,244,594; U.S. Pat. No. 5,194,416;U.S. Pat. No. 5,114,606; and European Pat. App. Pub. Nos. 549,271A1,549,272A1, 544,440A2, and 544,490A1; Preferred examples of thesecatalysts include Mn^(IV) ₂ (u-O)₃(1,4,7-trimethyl-1,4,7-triazacyclononane)₂ (PF₆)₂, Mn^(III) ₂ (u-O)₁(u-OAc)₂ (1,4,7-trimethyl-1,4,7-triazacyclononane)₂ (ClO₄)₂, Mn^(IV) ₄(u-O)₆ (1,4,7-triazacyclononane)₄ (ClO₄)₄, Mn^(III) Mn^(IV) ₄ (u-O)₁(u-OAc)₂ -(1,4,7-trimethyl-1,4,7-triazacyclononane)₂ (ClO₄)₃, Mn^(IV)(1,4,7-trimethyl-1,4,7-triazacyclononane)-(OCH₃)₃ (PF₆), and mixturesthereof. Other metal-based bleach catalysts include those disclosed inU.S. Pat. No. 4,430,243 and U.S. Pat. No. 5,114,611. The use ofmanganese with various complex ligands to enhance bleaching is alsoreported in the following U.S. Pat. Nos.: 4,728,455; 5,284,944;5,246,612; 5,256,779; 5,280,117; 5,274,147; 5,153,161; and 5,227,084.

As a practical matter, and not by way of limitation, the compositionsand processes herein can be adjusted to provide on the order of at leastone part per ten million of the active bleach catalyst species in theaqueous washing liquor, and will preferably provide from about 0.1 ppmto about 700 ppm, more preferably from about 1 ppm to about 500 ppm, ofthe catalyst species in the laundry liquor.

Cobalt bleach catalysts useful herein are known, and are described, forexample, in M. L. Tobe, "Base Hydrolysis of Transition-Metal Complexes",Adv. Inorg. Bioinorg. Mech., (1983), 2, pages 1-94. The most preferredcobalt catalyst useful herein are cobalt pentaamine acetate salts havingthe formula [Co(NH₃)₅ OAc] T_(y), wherein "OAc" represents an acetatemoiety and "T_(y) " is an anion, and especially cobalt pentaamineacetate chloride, [Co(NH₃)₅ OAc]Cl₂ ; as well as [Co(NH₃)₅ OAc](OAc)₂ ;[Co(NH₃)₅ OAc](PF₆)₂ ; [Co(NH₃)₅ OAc](SO₄); [Co(NH₃)₅ OAc](BF₄)₂ ; and[Co(NH₃)₅ OAc](NO₃)₂ (herein "PAC").

These cobalt catalysts are readily prepared by known procedures, such astaught for example in the Tobe article and the references cited therein,in U.S. Pat. No. 4,810,410, to Diakun et al, issued Mar. 7, 1989, J.Chem. Ed. (1989), 66 (12), 1043-45; The Synthesis and Characterizationof Inorganic Compounds, W. L. Jolly (Prentice-Hall; 1970), pp. 461-3;Inorg. Chem., 18, 1497-1502 (1979); Inorg. Chem., 21, 2881-2885 (1982);Inorg. Chem., 18, 2023-2025 (1979); Inorg. Synthesis, 173-176 (1960);and Journal of Physical Chemistry, 56, 22-25 (1952).

As a practical matter, and not by way of limitation, the compositionsand cleaning processes herein can be adjusted to provide on the order ofat least one part per hundred million of the active bleach catalystspecies in the aqueous washing medium, and will preferably provide fromabout 0.01 ppm to about 25 ppm, more preferably from about 0.05 ppm toabout 10 ppm, and most preferably from about 0.1 ppm to about 5 ppm, ofthe bleach catalyst species in the wash liquor. In order to obtain suchlevels in the wash liquor of an automatic washing process, typicalcompositions herein will comprise from about 0.0005% to about 0.2%, morepreferably from about 0.004% to about 0.08%, of bleach catalyst,especially manganese or cobalt catalysts, by weight of the cleaningcompositions.

Enzymes--Enzymes are preferably included in the present detergentcompositions for a variety of purposes, including removal ofprotein-based, carbohydrate-based, or triglyceride-based stains fromsubstrates, for the prevention of refugee dye transfer in fabriclaundering, and for fabric restoration. Suitable enzymes includeproteases, amylases, lipases, cellulases, peroxidases, and mixturesthereof of any suitable origin, such as vegetable, animal, bacterial,fungal and yeast origin. Preferred selections are influenced by factorssuch as pH-activity and/or stability optima, thermostability, andstability to active detergents, builders and the like. In this respectbacterial or fungal enzymes are preferred, such as bacterial amylasesand proteases, and fungal cellulases.

"Detersive enzyme", as used herein, means any enzyme having a cleaning,stain removing or otherwise beneficial effect in a laundry, hard surfacecleaning or personal care detergent composition. Preferred detersiveenzymes are hydrolases such as proteases, amylases and lipases.Preferred enzymes for laundry purposes include, but are not limited to,proteases, cellulases, lipases and peroxidases. Highly preferred forautomatic dishwashing are amylases and/or proteases, including bothcurrent commercially available types and improved types which, thoughmore and more bleach compatible though successive improvements, have aremaining degree of bleach deactivation susceptibility.

Enzymes are normally incorporated into detergent or detergent additivecompositions at levels sufficient to provide a "cleaning-effectiveamount". The term "cleaning effective amount" refers to any amountcapable of producing a cleaning, stain removal, soil removal, whitening,deodorizing, or freshness improving effect on substrates such asfabrics, dishware and the like. In practical terms for currentcommercial preparations, typical amounts are up to about 5 mg by weight,more typically 0.01 mg to 3 mg, of active enzyme per gram of thedetergent composition. Stated otherwise, the compositions herein willtypically comprise from 0.001% to 5%, preferably 0.01%-1% by weight of acommercial enzyme preparation. Protease enzymes are usually present insuch commercial preparations at levels sufficient to provide from 0.005to 0.1 Anson units (AU) of activity per gram of composition. For certaindetergents, such as in automatic dishwashing, it may be desirable toincrease the active enzyme content of the commercial preparation inorder to minimize the total amount of non-catalytically active materialsand thereby improve spotting/filming or other end-results. Higher activelevels may also be desirable in highly concentrated detergentformulations.

Suitable examples of proteases are the subtilisins which are obtainedfrom particular strains of B. subtilis and B. licheniformis. Onesuitable protease is obtained from a strain of Bacillus, having maximumactivity throughout the pH range of 8-12, developed and sold asESPERASE® by Novo Industries A/S of Denmark, hereinafter "Novo". Thepreparation of this enzyme and analogous enzymes is described in GB1,243,784 to Novo. Other suitable proteases include ALCALASE® andSAVINASE® from Novo and MAXATASE® from International Bio-Synthetics,Inc., The Netherlands; as well as Protease A as disclosed in EP 130,756A, Jan. 9, 1985 and Protease B as disclosed in EP 303,761 A, Apr. 28,1987 and EP 130,756 A, Jan. 9, 1985. See also a high pH protease fromBacillus sp. NCIMB 40338 described in WO 9318140 A to Novo. Enzymaticdetergents comprising protease, one or more other enzymes, and areversible protease inhibitor are described in WO 9203529 A to Novo.Other preferred proteases include those of WO 9510591 A to Procter &Gamble . When desired, a protease having decreased adsorption andincreased hydrolysis is available as described in WO 9507791 to Procter& Gamble. A recombinant trypsin-like protease for detergents suitableherein is described in WO 9425583 to Novo.

In more detail, an especially preferred protease, referred to as"Protease D" is a carbonyl hydrolase variant having an amino acidsequence not found in nature, which is derived from a precursor carbonylhydrolase by substituting a different amino acid for a plurality ofamino acid residues at a position in said carbonyl hydrolase equivalentto position +76, preferably also in combination with one or more aminoacid residue positions equivalent to those selected from the groupconsisting of +99, +101, +103, +104, +107, +123, +27, +105, +109, +126,+128, +135, +156, +166, +195, +197, +204, +206, +210, +216, +217, +218,+222, +260, +265, and/or +274 according to the numbering of Bacillusamyloliquefaciens subtilisin, as described in WO 95/10615 published Apr.20, 1995 by Genencor International.

Useful proteases are also described in PCT publications: WO 95/30010published Nov. 9, 1995 by The Procter & Gamble Company; WO 95/30011published Nov. 9, 1995 by The Procter & Gamble Company; WO 95/29979published Nov. 9, 1995 by The Procter & Gamble Company.

Amylases suitable herein, especially for, but not limited to automaticdishwashing purposes, include, for example, α-amylases described in GB1,296,839 to Novo; RAPIDASE®, International Bio-Synthetics, Inc. andTERMAMYL®, Novo. FUNGAMYL® from Novo is especially useful. Engineeringof enzymes for improved stability, e.g., oxidative stability, is known.See, for example J. Biological Chem., Vol. 260, No. 11, June 1985, pp.6518-6521. Certain preferred embodiments of the present compositions canmake use of amylases having improved stability in detergents such asautomatic dishwashing types, especially improved oxidative stability asmeasured against a reference-point of TERMAMYL® in commercial use in1993. These preferred amylases herein share the characteristic of being"stability-enhanced" amylases, characterized, at a minimum, by ameasurable improvement in one or more of: oxidative stability, e.g., tohydrogen peroxide/tetraacetylethylenediamine in buffered solution at pH9-10; thermal stability, e.g., at common wash temperatures such as about60° C.; or alkaline stability, e.g., at a pH from about 8 to about 11,measured versus the above-identified reference-point amylase. Stabilitycan be measured using any of the art-disclosed technical tests. See, forexample, references disclosed in WO 9402597. Stability-enhanced amylasescan be obtained from Novo or from Genencor International. One class ofhighly preferred amylases herein have the commonality of being derivedusing site-directed mutagenesis from one or more of the Bacillusamylases, especially the Bacillus α-amylases, regardless of whether one,two or multiple amylase strains are the immediate precursors. Oxidativestability-enhanced amylases vs. the above-identified reference amylaseare preferred for use, especially in bleaching, more preferably oxygenbleaching, as distinct from chlorine bleaching, detergent compositionsherein. Such preferred amylases include (a) an amylase according to thehereinbefore incorporated WO 9402597, Novo, Feb. 3, 1994, as furtherillustrated by a mutant in which substitution is made, using alanine orthreonine, preferably threonine, of the methionine residue located inposition 197 of the B. licheniformis alpha-amylase, known as TERMAMYL®,or the homologous position variation of a similar parent amylase, suchas B. amyloliquefaciens, B. subtilis, or B. stearothermophilus; (b)stability-enhanced amylases as described by Genencor International in apaper entitled "Oxidatively Resistant alpha-Amylases" presented at the207th American Chemical Society National Meeting, Mar. 13-17 1994, by C.Mitchinson. Therein it was noted that bleaches in automatic dishwashingdetergents inactivate alpha-amylases but that improved oxidativestability amylases have been made by Genencor from B. licheniformisNCIB8061. Methionine (Met) was identified as the most likely residue tobe modified. Met was substituted, one at a time, in positions 8, 15,197, 256, 304, 366 and 438 leading to specific mutants, particularlyimportant being M197L and M197T with the M197T variant being the moststable expressed variant. Stability was measured in CASCADE® andSUNLIGHT®; (c) particularly preferred amylases herein include amylasevariants having additional modification in the immediate parent asdescribed in WO 9510603 A and are available from the assignee, Novo, asDURAMYL®. Other particularly preferred oxidative stability enhancedamylase include those described in WO 9418314 to Genencor Internationaland WO 9402597 to Novo. Any other oxidative stability-enhanced amylasecan be used, for example as derived by site-directed mutagenesis fromknown chimeric, hybrid or simple mutant parent forms of availableamylases. Other preferred enzyme modifications are accessible. See WO9509909 A to Novo.

Other amylase enzymes include those described in WO 95/26397 and inco-pending application by Novo Nordisk PCT/DK96/00056. Specific amylaseenzymes for use in the detergent compositions of the present inventioninclude α-amylases characterized by having a specific activity at least25% higher than the specific activity of Termamyl® at a temperaturerange of 25° C. to 55° C. and at a pH value in the range of 8 to 10,measured by the Phadebas® α-amylase activity assay. (Such Phadebas®α-amylase activity assay is described at pages 9-10, WO 95/26397.) Alsoincluded herein are α-amylases which are at least 80% homologous withthe amino acid sequences shown in the SEQ ID listings in the references.These enzymes are preferably incorporated into laundry detergentcompositions at a level from 0.00018% to 0.060% pure enzyme by weight ofthe total composition, more preferably from 0.00024% to 0.048% pureenzyme by weight of the total composition.

Cellulases usable herein include both bacterial and fungal types,preferably having a pH optimum between 5 and 9.5. U.S. Pat. No.4,435,307, Barbesgoard et al, Mar. 6, 1984, discloses suitable fungalcellulases from Humicola insolens or Humicola strain DSM1800 or acellulase 212-producing fungus belonging to the genus Aeromonas, andcellulase extracted from the hepatopancreas of a marine mollusk,Dolabella Auricula Solander. Suitable cellulases are also disclosed inGB-A-2.075.028; GB-A-2.095.275 and DE-OS-2.247.832. CAREZYME® andCELLUZYME®(Novo) are especially useful. See also WO 9117243 to Novo.

Suitable lipase enzymes for detergent usage include those produced bymicroorganisms of the Pseudomonas group, such as Pseudomonas stutzeriATCC 19.154, as disclosed in GB 1,372,034. See also lipases in JapanesePatent Application 53,20487, laid open Feb. 24, 1978. This lipase isavailable from Amano Pharmaceutical Co. Ltd., Nagoya, Japan, under thetrade name Lipase P "Amano," or "Amano-P." Other suitable commerciallipases include Amano-CES, lipases ex Chromobacter viscosum, e.g.Chromobacter viscosum var. lipolyticum NRRLB 3673 from Toyo Jozo Co.,Tagata, Japan; Chromobacter viscosum lipases from U.S. BiochemicalCorp., U.S.A. and Disoynth Co., The Netherlands, and lipases exPseudomonas gladioli. LIPOLASE® enzyme derived from Humicola lanuginosaand commercially available from Novo, see also EP 341,947, is apreferred lipase for use herein. Lipase and amylase variants stabilizedagainst peroxidase enzymes are described in WO 9414951 A to Novo. Seealso WO 9205249 and RD 94359044.

In spite of the large number of publications on lipase enzymes, only thelipase derived from Humicola lanuginosa and produced in Aspergillusoryzae as host has so far found widespread application as additive forfabric washing products. It is available from Novo Nordisk under thetradename Lipolase™, as noted above. In order to optimize the stainremoval performance of Lipolase, Novo Nordisk have made a number ofvariants. As described in WO 92/05249, the D96L variant of the nativeHumicola lanuginosa lipase improves the lard stain removal efficiency bya factor 4.4 over the wild-type lipase (enzymes compared in an amountranging from 0.075 to 2.5 mg protein per liter). Research Disclosure No.35944 published on Mar. 10, 1994, by Novo Nordisk discloses that thelipase variant (D96L) may be added in an amount corresponding to0.001-100-mg (5-500,000 LU/liter) lipase variant per liter of washliquor. The present invention provides the benefit of improved whitenessmaintenance on fabrics using low levels of D96L variant in detergentcompositions containing the mid-chain branched surfactant surfactants inthe manner disclosed herein, especially when the D96L is used at levelsin the range of about 50 LU to about 8500 LU per liter of wash solution.

Cutinase enzymes suitable for use herein are described in WO 8809367 Ato Genencor.

Peroxidase enzymes may be used in combination with oxygen sources, e.g.,percarbonate, perborate, hydrogen peroxide, etc., for "solutionbleaching" or prevention of transfer of dyes or pigments removed fromsubstrates during the wash to other substrates present in the washsolution. Known peroxidases include horseradish peroxidase, ligninase,and haloperoxidases such as chloro-or bromo-peroxidase.Peroxidase-containing detergent compositions are disclosed in WO89099813 A, Oct. 19, 1989 to Novo and WO 8909813 A to Novo.

A range of enzyme materials and means for their incorporation intosynthetic detergent compositions is also disclosed in WO 9307263 A andWO 9307260 A to Genencor International, WO 8908694 A to Novo, and U.S.Pat. No. 3,553,139, Jan. 5, 1971 to McCarty et al. Enzymes are furtherdisclosed in U.S. Pat. No. 4,101,457, Place et al, Jul. 18, 1978, and inU.S. Pat. No. 4,507,219, Hughes, Mar. 26, 1985. Enzyme materials usefulfor liquid detergent formulations, and their incorporation into suchformulations, are disclosed in U.S. Pat. No. 4,261,868, Hora et al, Apr.14, 1981. Enzymes for use in detergents can be stabilised by varioustechniques. Enzyme stabilisation techniques are disclosed andexemplified in U.S. Pat. No. 3,600,319, Aug. 17, 1971, Gedge et al, EP199,405 and EP 200,586, Oct. 29, 1986, Venegas. Enzyme stabilisationsystems are also described, for example, in U.S. Pat. No. 3,519,570. Auseful Bacillus, sp. AC13 giving proteases, xylanases and cellulases, isdescribed in WO 9401532 A to Novo.

Enzyme Stabilizing System--The enzyme-containing compositions herein mayoptionally also comprise from about 0.001% to about 10%, preferably fromabout 0.005% to about 8%, most preferably from about 0.01% to about 6%,by weight of an enzyme stabilizing system. The enzyme stabilizing systemcan be any stabilizing system which is compatible with the detersiveenzyme. Such a system may be inherently provided by other formulationactives, or be added separately, e.g., by the formulator or by amanufacturer of detergent-ready enzymes. Such stabilizing systems can,for example, comprise calcium ion, boric acid, propylene glycol, shortchain carboxylic acids, boronic acids, and mixtures thereof, and aredesigned to address different stabilization problems depending on thetype and physical form of the detergent composition.

One stabilizing approach is the use of water-soluble sources of calciumand/or magnesium ions in the finished compositions which provide suchions to the enzymes. Calcium ions are generally more effective thanmagnesium ions and are preferred herein if only one type of cation isbeing used. Typical detergent compositions, especially liquids, willcomprise from about 1 to about 30, preferably from about 2 to about 20,more preferably from about 8 to about 12 millimoles of calcium ion perliter of finished detergent composition, though variation is possibledepending on factors including the multiplicity, type and levels ofenzymes incorporated. Preferably water-soluble calcium or magnesiumsalts are employed, including for example calcium chloride, calciumhydroxide, calcium formate, calcium malate, calcium maleate, calciumhydroxide and calcium acetate; more generally, calcium sulfate ormagnesium salts corresponding to the exemplified calcium salts may beused. Further increased levels of Calcium and/or Magnesium may of coursebe useful, for example for promoting the grease-cutting action ofcertain types of surfactant.

Another stabilizing approach is by use of borate species. See Severson,U.S. Pat. No. 4,537,706. Borate stabilizers, when used, may be at levelsof up to 10% or more of the composition though more typically, levels ofup to about 3% by weight of boric acid or other borate compounds such asborax or orthoborate are suitable for liquid detergent use. Substitutedboric acids such as phenylboronic acid, butaneboronic acid,p-bromophenylboronic acid or the like can be used in place of boric acidand reduced levels of total boron in detergent compositions may bepossible though the use of such substituted boron derivatives.

Stabilizing systems of certain cleaning compositions, for exampleautomatic dishwashing compositions, may further comprise from 0 to about10%, preferably from about 0.01% to about 6% by weight, of chlorinebleach scavengers, added to prevent chlorine bleach species present inmany water supplies from attacking and inactivating the enzymes,especially under alkaline conditions. While chlorine levels in water maybe small, typically in the range from about 0.5 ppm to about 1.75 ppm,the available chlorine in the total volume of water that comes incontact with the enzyme, for example during dish- or fabric-washing, canbe relatively large; accordingly, enzyme stability to chlorine in-use issometimes problematic. Since perborate or percarbonate, which have theability to react with chlorine bleach, may present in certain of theinstant compositions in amounts accounted for separately from thestabilizing system, the use of additional stabilizers against chlorine,may, most generally, not be essential, though improved results may beobtainable from their use. Suitable chlorine scavenger anions are widelyknown and readily available, and, if used, can be salts containingammonium cations with sulfite, bisulfite, thiosulfite, thiosulfate,iodide, etc. Antioxidants such as carbamate, ascorbate, etc., organicamines such as ethylenediaminetetracetic acid (EDTA) or alkali metalsalt thereof, monoethanolamine (MEA), and mixtures thereof can likewisebe used. Likewise, special enzyme inhibition systems can be incorporatedsuch that different enzymes have maximum compatibility. Otherconventional scavengers such as bisulfate, nitrate, chloride, sources ofhydrogen peroxide such as sodium perborate tetrahydrate, sodiumperborate monohydrate and sodium percarbonate, as well as phosphate,condensed phosphate, acetate, benzoate, citrate, formate, lactate,malate, tartrate, salicylate, etc., and mixtures thereof can be used ifdesired. In general, since the chlorine scavenger function can beperformed by ingredients separately listed under better recognizedfunctions, (e.g., hydrogen peroxide sources), there is no absoluterequirement to add a separate chlorine scavenger unless a compoundperforming that function to the desired extent is absent from anenzyme-containing embodiment of the invention; even then, the scavengeris added only for optimum results. Moreover, the formulator willexercise a chemist's normal skill in avoiding the use of any enzymescavenger or stabilizer which is majorly incompatible, as formulated,with other reactive ingredients. In relation to the use of ammoniumsalts, such salts can be simply admixed with the detergent compositionbut are prone to adsorb water and/or liberate ammonia during storage.Accordingly, such materials, if present, are desirably protected in aparticle such as that described in U.S. Pat. No. 4,652,392, Baginski etal.

Builders--Detergent builders selected from aluminosilicates andsilicates are preferably included in the compositions herein, forexample to assist in controlling mineral, especially Ca and/or Mg,hardness in wash water or to assist in the removal of particulate soilsfrom surfaces.

Suitable silicate builders include water-soluble and hydrous solid typesand including those having chain-, layer-, orthree-dimensional-structure as well as amorphous-solid ornon-structured-liquid types. Preferred are alkali metal silicates,particularly those liquids and solids having a SiO₂ :Na₂ O ratio in therange 1.6:1 to 3.2:1, including, particularly for automatic dishwashingpurposes, solid hydrous 2-ratio silicates marketed by PQ Corp. under thetradename BRITESIL®, e.g., BRITESIL H2O; and layered silicates, e.g.,those described in U.S. Pat. No. 4,664,839, May 12, 1987, H. P. Rieck.NaSKS-6, sometimes abbreviated "SKS-6", is a crystalline layeredaluminium-free δ-Na₂ SiO₅ morphology silicate marketed by Hoechst and ispreferred especially in granular laundry compositions. See preparativemethods in German DE-A-3,417,649 and DE-A-3,742,043. Other layeredsilicates, such as those having the general formula NaMSi_(x) O_(2x+1).yH₂ O wherein M is sodium or hydrogen, x is a number from 1.9 to 4,preferably 2, and y is a number from 0 to 20, preferably 0, can also oralternately be used herein. Layered silicates from Hoechst also includeNaSKS-5, NaSKS-7 and NaSKS-11, as the α, β and γ layer-silicate forms.Other silicates may also be useful, such as magnesium silicate, whichcan serve as a crispening agent in granules, as a stabilising agent forbleaches, and as a component of suds control systems.

Also suitable for use herein are synthesized crystalline ion exchangematerials or hydrates thereof having chain structure and a compositionrepresented by the following general formula in an anhydride form: xM₂O.ySiO₂.zM'O wherein M is Na and/or K, M' is Ca and/or Mg; y/x is 0.5 to2.0 and z/x is 0.005 to 1.0 as taught in U.S. Pat. No. 5,427,711,Sakaguchi et al, Jun. 27, 1995.

Aluminosilicate builders are especially useful in granular detergents,but can also be incorporated in liquids, pastes or gels. Suitable forthe present purposes are those having empirical formula: [M_(z)(AlO₂)_(z) (SiO₂)_(v) ].xH₂ O wherein z and v are integers of at least6, the molar ratio of z to v is in the range from 1.0 to 0.5, and x isan integer from 15 to 264. Aluminosilicates can be crystalline oramorphous, naturally-occurring or synthetically derived. Analuminosilicate production method is in U.S. Pat. No. 3,985,669,Krummel, et al, Oct. 12, 1976. Preferred synthetic crystallinealuminosilicate ion exchange materials are available as Zeolite A,Zeolite P (B), Zeolite X and, to whatever extent this differs fromZeolite P, the so-called Zeolite MAP. Natural types, includingclinoptilolite, may be used. Zeolite A has the formula: Na₁₂ [(AlO₂)₁₂(SiO₂)₁₂ ].xH₂ O wherein x is from 20 to 30, especially 27. Dehydratedzeolites (x=0-10) may also be used. Preferably, the aluminosilicate hasa particle size of 0.1-10 microns in diameter.

Additional Detergent Components

The detergent compositions of the invention may also contain additionaldetergent components. The precise nature of these additional components,and levels of incorporation thereof will depend on the physical form ofthe composition, and the precise nature of the washing operation forwhich it is to be used.

The compositions of the invention preferably contain one or moreadditional detergent components selected from surfactants, builders,alkalinity system, organic polymeric compounds, suds suppressors, soilsuspension and anti-redeposition agents and corrosion inhibitors.

Detersive Surfactants:

The detergent compositions according to the present invention preferablyfurther comprise additional surfactants, herein also referred to asco-surfactants, preferably selected from: anionic surfactants,preferably selected from the group of alkyl alkoxylated sulfates, alkylsulfates, and/or linear alkyl benzenesulfonate surfactants; cationicsurfactants, preferably selected from quaternary ammonium surfactants;nonionic surfactants, preferably alkyl ethoxylates, alkylpolyglucosides, and/or amine or amine oxide surfactants; amphotericsurfactants, preferably selected from betaines and/or polycarboxylates(for example polyglycinates); and zwiterionic surfactants.

A wide range of these co-surfactants can be used in the detergentcompositions of the present invention. A typical listing of anionic,nonionic, ampholytic and zwitterionic classes, and species of theseco-surfactants, is given in U.S. Pat. No. 3,664,961 issued to Norris onMay 23, 1972. Amphoteric surfactants are also described in detail in"Amphoteric Surfactants, Second Edition", E. G. Lomax, Editor (published1996, by Marcel Dekker, Inc.)

The laundry detergent compositions of the present invention typicallycomprise from about 0.1% to about 35%, preferably from about 0.5% toabout 15%, by weight of co-surfactants. Selected co-surfactants arefurther identified as follows.

(1) Anionic Co-surfactants:

Nonlimiting examples of anionic co-surfactants useful herein, typicallyat levels from about 0.1% to about 50%, by weight, include theconventional C₁₁ -C₁₈ alkyl benzene sulfonates ("LAS") and primary,branched-chain and random C₁₀ -C₂₀ alkyl sulfates ("AS"), the C₁₀ -C₁₈secondary (2,3) alkyl sulfates of the formula CH₃ (CH₂)_(x) (CHOSO₃ ⁻M⁺) CH₃ and CH₃ (CH₂)_(y) (CHOSO₃ ⁻ M⁺) CH₂ CH₃ where x and (y+1) areintegers of at least about 7, preferably at least about 9, and M is awater-solubilizing cation, especially sodium, unsaturated sulfates suchas oleyl sulfate, the C₁₀ -C₁₈ alpha-sulfonated fatty acid esters, theC₁₀ -C₁₈ sulfated alkyl polyglycosides, the C₁₀ -C₁₈ alkyl alkoxysulfates ("AE_(x) S"; especially EO 1-7 ethoxy sulfates), and C₁₀ -C₁₈alkyl alkoxy carboxylates (especially the EO 1-5 ethoxycarboxylates).The C₁₂ -C₁₈ betaines and sulfobetaines ("sultaines"), C₁₀ -C₁₈ amineoxides, and the like, can also be included in the overall compositions.C₁₀ -C₂₀ conventional soaps may also be used. If high sudsing isdesired, the branched-chain C₁₀ -C₁₆ soaps may be used. Otherconventional useful anionic co-surfactants are listed in standard texts.

The alkyl alkoxylated sulfate surfactants useful herein are preferablywater soluble salts or acids of the formula RO(A)_(m) SO₃ M wherein R isan unsubstituted C₁₀ -C₂₄ alkyl or hydroxyalkyl group having a C₁₀ -C₂₄alkyl component, preferably a C₁₂ -C₁₈ alkyl or hydroxyalkyl, morepreferably C₁₂ -C₁₅ alkyl or hydroxyalkyl, A is an ethoxy or propoxyunit, m is greater than zero, typically between about 0.5 and about 6,more preferably between about 0.5 and about 3, and M is H or a cationwhich can be, for example, a metal cation (e.g., sodium, potassium,lithium, calcium, magnesium, etc.), ammonium or substituted-ammoniumcation. Alkyl ethoxylated sulfates as well as alkyl propoxylatedsulfates are contemplated herein. Specific examples of substitutedammonium cations include ethanol-, triethanol-, methyl-, dimethyl,trimethyl-ammonium cations and quaternary ammonium cations such astetramethyl-ammonium and dimethyl piperidinium cations and those derivedfrom alkylamines such as ethylamine, diethylamine, triethylamine,mixtures thereof, and the like. Exemplary surfactants are C₁₂ -C₁₅ alkylpolyethoxylate (1.0) sulfate (C₁₂ -C₁₅ E(1.0)M), C₁₂ -C₁₅ alkylpolyethoxylate (2.25) sulfate (C₁₂ -C₁₅ E(2.25)M), C₁₂ C₁₅ alkylpolyethoxylate (3.0) sulfate (C₁₂ -C₁₅ E(3.0)M), and C₁₂ -C₁₅ alkylpolyethoxylate (4.0) sulfate (C₁₂ -C₁₅ E(4.0)M), wherein M isconveniently selected from sodium and potassium.

The alkyl sulfate surfactants useful herein are preferably water solublesalts or acids of the formula ROSO₃ M wherein R preferably is a C₁₀ -C₂₄hydrocarbyl, preferably an alkyl or hydroxyalkyl having a C₁₀ -C₁₈ alkylcomponent, more preferably a C₁₂ -C₁₅ alkyl or hydroxyalkyl, and M is Hor a cation, e.g., an alkali metal cation (e.g. sodium, potassium,lithium), or ammonium or substituted ammonium (e.g. methyl-, dimethyl-,and trimethyl ammonium cations and quaternary ammonium cations such astetramethyl-ammonium and dimethyl piperidinium cations and quaternaryammonium cations derived from alkylamines such as ethylamine,diethylamine, triethylamine, and mixtures thereof, and the like).

Other suitable anionic surfactants that can be used are alkyl estersulfonate surfactants including linear esters of C₈ -C₂₀ carboxylicacids (i.e., fatty acids) which are sulfonated with gaseous SO₃according to "The Journal of the American Oil Chemists Society", 52(1975), pp. 323-329. Suitable starting materials would include naturalfatty substances as derived from tallow, palm oil, etc.

The preferred alkyl ester sulfonate surfactant, especially for laundryapplications, comprise alkyl ester sulfonate surfactants of thestructural formula:

    R.sup.3 --CH(SO.sub.3 M)--C(O)--OR.sup.4

wherein R³ is a C₈ -C₂₀ hydrocarbyl, preferably an alkyl, or combinationthereof, R⁴ is a C₁ -C₆ hydrocarbyl, preferably an alkyl, or combinationthereof, and M is a cation which forms a water soluble salt with thealkyl ester sulfonate. Suitable salt-forming cations include metals suchas sodium, potassium, and lithium, and substituted or unsubstitutedammonium cations, such as monoethanolamine, diethanolamine, andtriethanolamine. Preferably, R³ is C₁₀ -C₁₆ alkyl, and R⁴ is methyl,ethyl or isopropyl. Especially preferred are the methyl ester sulfonateswherein R³ is C₁₀ -C₁₆ alkyl.

Other anionic co-surfactants useful for detersive purposes can also beincluded in the laundry detergent compositions of the present invention.These can include salts (including, for example, sodium, potassium,ammonium, and substituted ammonium salts such as mono-, di- andtriethanolamine salts) of soap, C₈ -C₂₂ primary of secondaryalkanesulfonates, C₈ -C₂₄ olefinsulfonates, sulfonated polycarboxylicacids prepared by sulfonation of the pyrolyzed product of alkaline earthmetal citrates, e.g., as described in British patent specification No.1,082,179, C₈ -C₂₄ alkylpolyglycolethersulfates (containing up to 10moles of ethylene oxide); alkyl glycerol sulfonates, fatty acyl glycerolsulfonates, fatty oleoyl glycerol sulfates, alkyl phenol ethylene oxideether sulfates, paraffin sulfonates, alkyl phosphates, isethionates suchas the acyl isethionates, N-acyl taurates, alkyl succinamates andsulfosuccinates, monoesters of sulfosuccinates (especially saturated andunsaturated C₁₂ -C₁₈ monoesters) and diesters of sulfosuccinates(especially saturated and unsaturated C₆ -C₁₂ diesters), sulfates ofalkylpolysaccharides such as the sulfates of alkylpolyglucoside (thenonionic nonsulfated compounds being described below), and alkylpolyethoxy carboxylates such as those of the formula RO(CH₂ CH₂ O)_(k)--CH₂ COO--M+ wherein R is a C₈ -C₂₂ alkyl, k is an integer from 0 to10, and M is a soluble salt-forming cation. Resin acids and hydrogenatedresin acids are also suitable, such as rosin, hydrogenated rosin, andresin acids and hydrogenated resin acids present in or derived from talloil. Further examples are described in "Surface Active Agents andDetergents" (Vol. I and II by Schwartz, Perry and Berch). A variety ofsuch surfactants are also generally disclosed in U.S. Pat. No.3,929,678, issued Dec. 30, 1975 to Laughlin, et al. at Column 23, line58 through Column 29, line 23 (herein incorporated by reference).

A preferred disulfate surfactant has the formula ##STR33## where R is analkyl, substituted alkyl, alkenyl, aryl, alkaryl, ether, ester, amine oramide group of chain length C₁ to C₂₈, preferably C₃ to C₂₄, mostpreferably C₈ to C₂₀, or hydrogen; A and B are independently selectedfrom alkyl, substituted alkyl, and alkenyl groups of chain length C₁ toC₂₈, preferably C₁ to C₅, most preferably C₁ or C₂, or a covalent bond,and A and B in total contain at least 2 atoms; A, B, and R in totalcontain from 4 to about 31 carbon atoms; X and Y are anionic groupsselected from the group consisting of sulfate and sulfonate, providedthat at least one of X or Y is a sulfate group; and M is a cationicmoiety, preferably a substituted or unsubstituted ammonium ion, or analkali or alkaline earth metal ion.

The most preferred disulfate surfactant has the formula as above where Ris an alkyl group of chain length from C₁₀ to C₁₈, A and B areindependently C₁ or C₂, both X and Y are sulfate groups, and M is apotassium, ammonium, or a sodium ion.

The disulfate surfactant is typically present at levels of incorporationof from about 0.1% to about 50%, preferably from about 0.1% to about35%, most preferably from about 0.5% to about 15% by weight of thedetergent composition.

Preferred disulfate surfactant herein include:

(a) 1,3 disulfate compounds, preferably 1,3 C7-C23 (i.e., the totalnumber of carbons in the molecule) straight or branched chain alkyl oralkenyl disulfates, more preferably having the formula: ##STR34##wherein R is a straight or branched chain alkyl or alkenyl group ofchain length from about C₄ to about C_(18;)

(b) 1,4 disulfate compounds, preferably 1,4 C8-C22 straight or branchedchain alkyl or alkenyl disulfates, more preferably having the formula:##STR35## wherein R is a straight or branched chain alkyl or alkenylgroup of chain length from about C₄ to about C₁₈ ; preferred R areselected from octanyl, nonanyl, decyl, dodecyl, tetradecyl, hexadecyl,octadecyl, and mixtures thereof; and

(c) 1,5 disulfate compounds, preferably 1,5 C9-C23 straight or branchedchain alkyl or alkenyl disulfates, more preferably having the formula:##STR36## wherein R is a straight or branched chain alkyl or alkenylgroup of chain length from about C₄ to about C₁₈.

Known syntheses of certain disulfated surfactants, in general, use analkyl or alkenyl succinic anhydride as the principal starting material.This is initially subjected to a reduction step from which a diol isobtained. Subsequently the diol is subjected to a sulfation step to givethe disulfated product. As an example, U.S. Pat. No. 3,634,269 describes2-alkyl or alkenyl-1,4-butanediol disulfates prepared by the reductionof alkenyl succinic anhydrides with lithium aluminium hydride to produceeither alkenyl or alkyl diols which are then sulfated. In addition, U.S.Pat. No. 3,959,334 and U.S. Pat. No. 4,000,081 describe2-hydrocarbyl-1,4-butanediol disulfates also prepared using a methodinvolving the reduction of alkenyl succinic anhydrides with lithiumaluminium hydride to produce either alkenyl or alkyl diols which arethen sulfated.

See also U.S. Pat. No. 3,832,408 and U.S. Pat. No. 3,860,625 whichdescribe 2-alkyl or alkenyl-1,4-butanediol ethoxylate disulfatesprepared by the reduction of alkenyl succinic anhydrides with lithiumaluminium hydride to produce either alkenyl or alkyl diols which arethen ethoxylated prior to sulfation.

These compounds may also be made by a method involving synthesis of thedisulfate surfactant from a substituted cyclic anhydride having one ormore carbon chain substituents having in total at least 5 carbon atomscomprising the following steps:

(i) reduction of said substituted cyclic anhydride to form a diol; and

(ii) sulfation of said diol to form a disulfate

wherein said reduction step comprises hydrogenation under pressure inthe presence of a transition metal-containing hydrogenation catalyst.

When included therein, the laundry detergent compositions of the presentinvention typically comprise from about 0.1% to about 50%, preferablyfrom about 1% to about 40% by weight of an anionic surfactant.

(2) Nonionic Co-surfactants:

Nonlimiting examples of nonionic co-surfactants useful herein typicallyat levels from about 0.1% to about 50%, by weight include thealkoxylated alcohols (AE's) and alkyl phenols, polyhydroxy fatty acidamides (PFAA's), alkyl polyglycosides (APG's), C₁₀ -C₁₈ glycerol ethers,and the like.

More specifically, the condensation products of primary and secondaryaliphatic alcohols with from about 1 to about 25 moles of ethylene oxide(AE) are suitable for use as the nonionic surfactant in the presentinvention. The alkyl chain of the aliphatic alcohol can either bestraight or branched, primary or secondary, and generally contains fromabout 8 to about 22 carbon atoms. Preferred are the condensationproducts of alcohols having an alkyl group containing from about 8 toabout 20 carbon atoms, more preferably from about 10 to about 18 carbonatoms, with from about 1 to about 10 moles, preferably 2 to 7, mostpreferably 2 to 5, of ethylene oxide per mole of alcohol. Especiallypreferred nonionic surfactants of this type are the C₉ -C₁₅ primaryalcohol ethoxylates containing 3-12 moles of ethylene oxide per mole ofalcohol, particularly the C₁₂ -C₁₅ primary alcohols containing 5-10moles of ethylene oxide per mole of alcohol.

Examples of commercially available nonionic surfactants of this typeinclude: Tergitol™ 15-S-9 (the condensation product of C₁₁ -C₁₅ linearalcohol with 9 moles ethylene oxide) and Tergitol™ 24-L-6 NMW (thecondensation product of C₁₂ -C₁₄ primary alcohol with 6 moles ethyleneoxide with a narrow molecular weight distribution), both marketed byUnion Carbide Corporation; Neodol™ 45-9 (the condensation product of C₁₄-C₁₅ linear alcohol with 9 moles of ethylene oxide), Neodol™ 23-3 (thecondensation product of C₁₂ -C₁₃ linear alcohol with 3 moles of ethyleneoxide), Neodol™ 45-7 (the condensation product of C₁₄ -C₁₅ linearalcohol with 7 moles of ethylene oxide) and Neodol™ 45-5 (thecondensation product of C₁₄ -C₁₅ linear alcohol with 5 moles of ethyleneoxide) marketed by Shell Chemical Company; Kyro™ EOB (the condensationproduct of C₁₃ -C₁₅ alcohol with 9 moles ethylene oxide), marketed byThe Procter & Gamble Company; and Genapol LA O3O or O5O (thecondensation product of C₁₂ -C₁₄ alcohol with 3 or 5 moles of ethyleneoxide) marketed by Hoechst. The preferred range of HLB in these AEnonionic surfactants is from 8-17 and most preferred from 8-14.Condensates with propylene oxide and butylene oxides may also be used.

Another class of preferred nonionic co-surfactants for use herein arethe polyhydroxy fatty acid amide surfactants of the formula. ##STR37##wherein R¹ is H, or C₁₋₄ hydrocarbyl, 2-hydroxy ethyl, 2-hydroxy propylor a mixture thereof, R² is C₅₋₃₁ hydrocarbyl, and Z is apolyhydroxyhydrocarbyl having a linear hydrocarbyl chain with at least 3hydroxyls directly connected to the chain, or an alkoxylated derivativethereof. Preferably, R¹ is methyl, R² is a straight C₁₁₋₁₅ alkyl orC₁₅₋₁₇ alkyl or alkenyl chain such as coconut alkyl or mixtures thereof,and Z is derived from a reducing sugar such as glucose, fructose,maltose, lactose, in a reductive amination reaction. Typical examplesinclude the C₁₂ -C₁₈ and C₁₂ -C₁₄ N-methylglucamides. See U.S. Pat. Nos.5,194,639 and 5,298,636. N-alkoxy polyhydroxy fatty acid amides can alsobe used; see U.S. Pat. No. 5,489,393.

Also useful as a nonionic co-surfactant in the present invention are thealkylpolysaccharides such as those disclosed in U.S. Pat. No. 4,565,647,Llenado, issued Jan. 21, 1986, having a hydrophobic group containingfrom about 6 to about 30 carbon atoms, preferably from about 10 to about16 carbon atoms, and a polysaccharide, e.g. a polyglycoside, hydrophilicgroup containing from about 1.3 to about 10, preferably from about 1.3to about 3, most preferably from about 1.3 to about 2.7 saccharideunits. Any reducing saccharide containing 5 or 6 carbon atoms can beused, e.g., glucose, galactose and galactosyl moieties can besubstituted for the glucosyl moieties (optionally the hydrophobic groupis attached at the 2-, 3-, 4-, etc. positions thus giving a glucose orgalactose as opposed to a glucoside or galactoside). The intersaccharidebonds can be, e.g., between the one position of the additionalsaccharide units and the 2-, 3-, 4-, and/or 6-positions on the precedingsaccharide units.

Preferred alkylpolyglycosides have the formula

    R.sup.2 O(C.sub.n H.sub.2n O).sub.t (glycosyl).sub.x

wherein R² is selected from the group consisting of alkyl, alkylphenyl,hydroxyalkyl, hydroxyalkylphenyl, and mixtures thereof in which thealkyl groups contain from about 10 to about 18, preferably from about 12to about 14, carbon atoms; n is 2 or 3, preferably 2; t is from 0 toabout 10, preferably 0; and x is from about 1.3 to about 10, preferablyfrom about 1.3 to about 3, most preferably from about 1.3 to about 2.7.The glycosyl is preferably derived from glucose. To prepare thesecompounds, the alcohol or alkylpolyethoxy alcohol is formed first andthen reacted with glucose, or a source of glucose, to form the glucoside(attachment at the 1-position). The additional glycosyl units can thenbe attached between their 1-position and the preceding glycosyl units2-, 3-, 4- and/or 6-position, preferably predominately the 2-position.Compounds of this type and their use in detergent are disclosed in EP-B0 070 077, 0 075 996 and 0 094 118.

Polyethylene, polypropylene, and polybutylene oxide condensates of alkylphenols are also suitable for use as the nonionic surfactant of thesurfactant systems of the present invention, with the polyethylene oxidecondensates being preferred. These compounds include the condensationproducts of alkyl phenols having an alkyl group containing from about 6to about 14 carbon atoms, preferably from about 8 to about 14 carbonatoms, in either a straight-chain or branched-chain configuration withthe alkylene oxide. In a preferred embodiment, the ethylene oxide ispresent in an amount equal to from about 2 to about 25 moles, morepreferably from about 3 to about 15 moles, of ethylene oxide per mole ofalkyl phenol. Commercially available nonionic surfactants of this typeinclude Igepal™ CO-630, marketed by the GAF Corporation; and Triton™X-45, X-114, X-100 and X-102, all marketed by the Rohm & Haas Company.These surfactants are commonly referred to as alkylphenol alkoxylates(e.g., alkyl phenol ethoxylates).

The condensation products of ethylene oxide with a hydrophobic baseformed by the condensation of propylene oxide with propylene glycol arealso suitable for use as the additional nonionic surfactant in thepresent invention. The hydrophobic portion of these compounds willpreferably have a molecular weight of from about 1500 to about 1800 andwill exhibit water insolubility. The addition of polyoxyethylenemoieties to this hydrophobic portion tends to increase the watersolubility of the molecule as a whole, and the liquid character of theproduct is retained up to the point where the polyoxyethylene content isabout 50% of the total weight of the condensation product, whichcorresponds to condensation with up to about 40 moles of ethylene oxide.Examples of compounds of this type include certain of thecommercially-available Pluronic™ surfactants, marketed by BASF.

Also suitable for use as the nonionic surfactant of the nonionicsurfactant system of the present invention, are the condensationproducts of ethylene oxide with the product resulting from the reactionof propylene oxide and ethylenediamine. The hydrophobic moiety of theseproducts consists of the reaction product of ethylenediamine and excesspropylene oxide, and generally has a molecular weight of from about 2500to about 3000. This hydrophobic moiety is condensed with ethylene oxideto the extent that the condensation product contains from about 40% toabout 80% by weight of polyoxyethylene and has a molecular weight offrom about 5,000 to about 11,000. Examples of this type of nonionicsurfactant include certain of the commercially available Tetronic™compounds, marketed by BASF.

Also preferred nonionics are amine oxide surfactants. The compositionsof the present invention may comprise amine oxide in accordance with thegeneral formula I:

    R.sup.1 (EO).sub.x (PO).sub.y (BO).sub.z N(O)(CH.sub.2 R').sub.2·q H.sub.2 O                                                 (I).

In general, it can be seen that the structure (I) provides onelong-chain moiety R¹ (EO)_(x) (PO)_(y) (BO)_(z) and two short chainmoieties, CH₂ R'. R' is preferably selected from hydrogen, methyl and--CH₂ OH. In general R¹ is a primary or branched hydrocarbyl moietywhich can be saturated or unsaturated, preferably, R¹ is a primary alkylmoiety. When x+y+z=0, R¹ is a hydrocarbyl moiety having chainlength offrom about 8 to about 18. When x+y+z is different from 0, R¹ may besomewhat longer, having a chainlength in the range C₁₂ -C₂₄. The generalformula also encompasses amine oxides wherein x+y+z=0, R₁ =C₈ -C₁₈, R'=Hand q=0-2, preferably 2. These amine oxides are illustrated by C₁₂₋₁₄alkyldimethyl amine oxide, hexadecyl dimethylamine oxide, octadecylamineoxide and their hydrates, especially the dihydrates as disclosed in U.S.Pat. Nos. 5,075,501 and 5,071,594, incorporated herein by reference.

The invention also encompasses amine oxides wherein x+y+z is differentfrom zero, specifically x+y+z is from about 1 to about 10, R¹ is aprimary alkyl group containing 8 to about 24 carbons, preferably fromabout 12 to about 16 carbon atoms; in these embodiments y+z ispreferably 0 and x is preferably from about 1 to about 6, morepreferably from about 2 to about 4; EO represents ethyleneoxy; POrepresents propyleneoxy; and BO represents butyleneoxy. Such amineoxides can be prepared by conventional synthetic methods, e.g., by thereaction of alkylethoxysulfates with dimethylamine followed by oxidationof the ethoxylated amine with hydrogen peroxide.

Highly preferred amine oxides herein are solutions at ambienttemperature. Amine oxides suitable for use herein are made commerciallyby a number of suppliers, including Akzo Chemie, Ethyl Corp., andProcter & Gamble. See McCutcheon's compilation and Kirk-Othmer reviewarticle for alternate amine oxide manufacturers.

Whereas in certain of the preferred embodiments R' is H, there is somelatitude with respect to having R' slightly larger than H. Specifically,the invention further encompasses embodiments wherein R' is CH₂ OH, suchas hexadecylbis(2-hydroxyethyl)amine oxide,tallowbis(2-hydroxyethyl)amine oxide, stearylbis(2-hydroxyethyl)amineoxide and oleylbis(2-hydroxyethyl)amine oxide, dodecyldimethylamineoxide dihydrate.

(3) Cationic Co-surfactants:

Nonlimiting examples of cationic co-surfactants useful herein typicallyat levels from about 0.1% to about 50%, by weight include the cholineester-type quats and alkoxylated quaternary ammonium (AQA) surfactantcompounds, and the like.

Cationic co-surfactants useful as a component of the surfactant systemis a cationic choline ester-type quat surfactant which are preferablywater dispersible compounds having surfactant properties and comprise atleast one ester (i.e. --COO--) linkage and at least one cationicallycharged group. Suitable cationic ester surfactants, including cholineester surfactants, have for example been disclosed in U.S. Pat. Nos.4,228,042, 4,239,660 and 4,260,529.

Preferred cationic ester surfactants are those having the formula:##STR38## wherein R₁ is a C₅ -C₃₁ linear or branched alkyl, alkenyl oralkaryl chain or M⁻ N⁺ (R₆ R₇ R₈)(CH₂)_(s) ; X and Y, independently, areselected from the group consisting of COO, OCO, O, CO, OCOO, CONH, NHCO,OCONH and NHCOO wherein at least one of X or Y is a COO, OCO, OCOO,OCONH or NHCOO group; R₂, R₃, R₄, R₆, R₇ and R₈ are independentlyselected from the group consisting of alkyl, alkenyl, hydroxyalkyl,hydroxyalkenyl and alkaryl groups having from 1 to 4 carbon atoms; andR₅ is independently H or a C₁ -C₃ alkyl group; wherein the values of m,n, s and t independently lie in the range of from 0 to 8, the value of blies in the range from 0 to 20, and the values of a, u and vindependently are either 0 or 1 with the proviso that at least one of uor v must be 1; and wherein M is a counter anion.

Preferably R₂, R₃ and R₄ are independently selected from CH₃ and --CH₂CH₂ OH.

Preferably M is selected from the group consisting of halide, methylsulfate, sulfate, and nitrate, more preferably methyl sulfate, chloride,bromide or iodide.

Preferred water dispersible cationic ester surfactants are the cholineesters having the formula: ##STR39## wherein R₁ is a C₁₁ -C₁₉ linear orbranched alkyl chain.

Particularly preferred choline esters of this type include the stearoylcholine ester quaternary methylammonium halides (R¹ ═C₁₇ alkyl),palmitoyl choline ester quaternary methylammonium halides (R¹ ═C₁₅alkyl), myristoyl choline ester quaternary methylammonium halides (R¹═C₁₃ alkyl), lauroyl choline ester quaternary methylammonium halides (R¹═C₁₁ alkyl), cocoyl choline ester quaternary methylammonium halides (R¹═C₁₁ -C₁₃ alkyl), tallowyl choline ester quaternary methylammoniumhalides (R¹ ═C₁₅ -C₁₇ alkyl), and any mixtures thereof.

The particularly preferred choline esters, given above, may be preparedby the direct esterification of a fatty acid of the desired chain lengthwith dimethylaminoethanol, in the presence of an acid catalyst. Thereaction product is then quaternized with a methyl halide, preferably inthe presence of a solvent such as ethanol, propylene glycol orpreferably a fatty alcohol ethoxylate such as C₁₀ -C₁₈ fatty alcoholethoxylate having a degree of ethoxylation of from 3 to 50 ethoxy groupsper mole forming the desired cationic material. They may also beprepared by the direct esterification of a long chain fatty acid of thedesired chain length together with 2-haloethanol, in the presence of anacid catalyst material. The reaction product is then quaternized withtrimethylamine, forming the desired cationic material.

Other suitable cationic ester surfactants have the structural formulasbelow, wherein d may be from 0 to 20. ##STR40## In a preferred aspectthese cationic ester surfactant are hydrolysable under the conditions ofa laundry wash method.

Cationic co-surfactants useful herein also include alkoxylatedquaternary ammonium (AQA) surfactant compounds (referred to hereinafteras "AQA compounds") having the formula: ##STR41## wherein R¹ is an alkylor alkenyl moiety containing from about 8 to about 18 carbon atoms,preferably 10 to about 16 carbon atoms, most preferably from about 10 toabout 14 carbon atoms; R² is an alkyl group containing from one to threecarbon atoms, preferably methyl; R³ and R⁴ can vary independently andare selected from hydrogen (preferred), methyl and ethyl; X⁻ is an anionsuch as chloride, bromide, methylsulfate, sulfate, or the like,sufficient to provide electrical neutrality. A and A' can varyindependently and are each selected from C₁ -C₄ alkoxy, especiallyethoxy (i.e., --CH₂ CH₂ O--), propoxy, butoxy and mixed ethoxy/propoxy;p is from 0 to about 30, preferably 1 to about 4 and q is from 0 toabout 30, preferably 1 to about 4, and most preferably to about 4;preferably both p and q are 1. See also: EP 2,084, published May 30,1979, by The Procter & Gamble Company, which describes cationicco-surfactants of this type which are also useful herein.

AQA compounds wherein the hydrocarbyl substituent R¹ is C₈ -C₁₁,especially C₁₀, enhance the rate of dissolution of laundry granules,especially under cold water conditions, as compared with the higherchain length materials. Accordingly, the C₈ -C₁₁ AQA surfactants may bepreferred by some formulators. The levels of the AQA surfactants used toprepare finished laundry detergent compositions can range from about0.1% to about 5%, typically from about 0.45% to about 2.5%, by weight.

According to the foregoing, the following are nonlimiting, specificillustrations of AQA surfactants used herein. It is to be understoodthat the degree of alkoxylation noted herein for the AQA surfactants isreported as an average, following common practice for conventionalethoxylated nonionic surfactants. This is because the ethoxylationreactions typically yield mixtures of materials with differing degreesof ethoxylation. Thus, it is not uncommon to report total EO valuesother than as whole numbers, e.g., "EO2.5", "EO3.5", and the like.

    ______________________________________                                        Designation R.sup.1  R.sup.2 ApR.sup.3                                                                              A'qR.sup.4                              ______________________________________                                        AQA-1       C.sub.12 -C.sub.14                                                                     CH.sub.3                                                                              EO       EO                                        (also referred to as                                                          Coco Methyl EO2)                                                              AQA-2 C.sub.12 -C.sub.16 CH.sub.3 (EO).sub.2 EO                               AQA-3 C.sub.12 -C.sub.14 CH.sub.3 (EO).sub.2 (EO).sub.2                       (Coco Methyl EO4)                                                             AQA-4 C.sub.12 CH.sub.3 EO EO                                                 AQA-5 C.sub.12 -C.sub.14 CH.sub.3 (EO).sub.2 (EO).sub.3                       AQA-6 C.sub.12 -C.sub.14 CH.sub.3 (EO).sub.2 (EO).sub.3                       AQA-7 C.sub.8 -C.sub.18 CH.sub.3 (EO).sub.3 (EO).sub.2                        AQA-8 C.sub.12 -C.sub.14 CH.sub.3 (EO).sub.4 (EO).sub.4                       AQA-9 C.sub.12 -C.sub.14 C.sub.2 H.sub.5 (EO).sub.3 (EO).sub.3                AQA-10 C.sub.12 -C.sub.18 C.sub.3 H.sub.7 (EO).sub.3 (EO).sub.4                                                    AQA-11 C.sub.12 -C.sub.18 CH.sub.3                                           (propoxy) (EO).sub.3                      AQA-12 C.sub.10 -C.sub.18 C.sub.2 H.sub.5 (iso-propoxy).sub.2 (EO).sub.3      AQA-13 C.sub.10 -C.sub.18 CH.sub.3 (EO/PO).sub.2 (EO).sub.3                   AQA-14 C.sub.8 -C.sub.18 CH.sub.3 (EO).sub.15 * (EO).sub.15 *                 AQA-15 C.sub.10 CH.sub.3 EO EO                                                AQA-16 C.sub.8 -C.sub.12 CH.sub.3 EO EO                                     AQA-17      C.sub.9 -C.sub.11                                                                      CH.sub.3                                                                              EO 3.5 Avg.                                        AQA-18 C.sub.12 CH.sub.3 EO 3.5 Avg.                                        AQA-19      C.sub.8 -C.sub.14                                                                      CH.sub.3                                                                              (EO).sub.10                                                                            (EO).sub.10                               AQA-20 C.sub.10 C.sub.2 H.sub.5 (EO).sub.2 (EO).sub.3                         AQA-21 C.sub.12 -C.sub.14 C.sub.2 H.sub.5 (EO).sub.5 (EO).sub.3                                                    AQA-22 C.sub.12 -C.sub.18 C.sub.3                                            H.sub.7 Bu (EO).sub.2                   ______________________________________                                         *Ethoxy, optionally endcapped with methyl or ethyl.                      

The preferred bis-ethoxylated cationic surfactants herein are availableunder the trade name ETHOQUAD from Akzo Nobel Chemicals Company.

Highly preferred bis-AQA compounds for use herein are of the formula##STR42## wherein R¹ is C₁₀ -C₁₈ hydrocarbyl and mixtures thereof,preferably C₁₀, C₁₂, C₁₄ alkyl and mixtures thereof, and X is anyconvenient anion to provide charge balance, preferably chloride. Withreference to the general AQA structure noted above, since in a preferredcompound R¹ is derived from coconut (C₁₂ -C₁₄ alkyl) fraction fattyacids, R² is methyl and ApR³ and A'qR⁴ are each monoethoxy, thispreferred type of compound is referred to herein as "CocoMeEO2" or"AQA-1" in the above list.

Other preferred AQA compounds herein include compounds of the formula:##STR43## wherein R¹ is C₁₀ -C₁₈ hydrocarbyl, preferably C₁₀ -C₁₄ alkyl,independently p is 1 to about 3 and q is 1 to about 3, R² is C₁ -C₃alkyl, preferably methyl, and X is an anion, especially chloride.

Other compounds of the foregoing type include those wherein the ethoxy(CH₂ CH₂ O) units (EO) are replaced by butoxy (Bu), isopropoxy[CH(CH₃)CH₂ O] and [CH₂ CH(CH₃ O] units (i-Pr) or n-propoxy units (Pr),or mixtures of EO and/or Pr and/or i-Pr units.

The following illustrates various other adjunct ingredients which may beused in the compositions of this invention, but is not intended to belimiting thereof. While the combination of the mid-chain branchedsurfactant surfactants with such adjunct compositional ingredients canbe provided as finished products in the form of liquids, gels, bars, orthe like using conventional techniques, the manufacture of the granularlaundry detergents herein requires some special processing techniques inorder to achieve optimal performance. Accordingly, the manufacture oflaundry granules will be described hereinafter separately in theGranules Manufacture section (below), for the convenience of theformulator.

Additional Builders--Detergent builders in place of or in addition tothe silicates and aluminosilicates described hereinbefore can optionallybe included in the compositions herein, for example to assist incontrolling mineral, especially Ca and/or Mg, hardness in wash water orto assist in the removal of particulate soils from surfaces. Builderscan operate via a variety of mechanisms including forming soluble orinsoluble complexes with hardness ions, by ion exchange, and by offeringa surface more favorable to the precipitation of hardness ions than arethe surfaces of articles to be cleaned. Builder level can vary widelydepending upon end use and physical form of the composition. Builtdetergents typically comprise at least about 1% builder. Liquidformulations typically comprise about 5% to about 50%, more typically 5%to 35% of builder. Granular formulations typically comprise from about10% to about 80%, more typically 15% to 50% builder by weight of thedetergent composition. Lower or higher levels of builders are notexcluded. For example, certain detergent additive or high-surfactantformulations can be unbuilt.

Suitable builders herein can be selected from the group consisting ofphosphates and polyphosphates, especially the sodium salts; carbonates,bicarbonates, sesquicarbonates and carbonate minerals other than sodiumcarbonate or sesquicarbonate; organic mono-, di-, tri-, andtetracarboxylates especially water-soluble nonsurfactant carboxylates inacid, sodium, potassium or alkanolammonium salt form, as well asoligomeric or water-soluble low molecular weight polymer carboxylatesincluding aliphatic and aromatic types; and phytic acid. These may becomplemented by borates, e.g., for pH-buffering purposes, or bysulfates, especially sodium sulfate and any other fillers or carrierswhich may be important to the engineering of stable surfactant and/orbuilder-containing detergent compositions.

Builder mixtures, sometimes termed "builder systems" can be used andtypically comprise two or more conventional builders, optionallycomplemented by chelants, pH-buffers or fillers, though these lattermaterials are generally accounted for separately when describingquantities of materials herein. In terms of relative quantities ofsurfactant and builder in the present detergents, preferred buildersystems are typically formulated at a weight ratio of surfactant tobuilder of from about 60:1 to about 1:80. Certain preferred laundrydetergents have said ratio in the range 0.90:1.0 to 4.0:1.0, morepreferably from 0.95:1.0 to 3.0:1.0.

P-containing detergent builders often preferred where permitted bylegislation include, but are not limited to, the alkali metal, ammoniumand alkanolammonium salts of polyphosphates exemplified by thetripolyphosphates, pyrophosphates, glassy polymeric meta-phosphates; andphosphonates.

Suitable carbonate builders include alkaline earth and alkali metalcarbonates as disclosed in German Patent Application No. 2,321,001published on Nov. 15, 1973, although sodium bicarbonate, sodiumcarbonate, sodium sesquicarbonate, and other carbonate minerals such astrona or any convenient multiple salts of sodium carbonate and calciumcarbonate such as those having the composition 2Na₂ CO₃.CaCO₃ whenanhydrous, and even calcium carbonates including calcite, aragonite andvaterite, especially forms having high surface areas relative to compactcalcite may be useful, for example as seeds or for use in syntheticdetergent bars.

Suitable organic detergent builders include polycarboxylate compounds,including water-soluble nonsurfactant dicarboxylates andtricarboxylates. More typically builder polycarboxylates have aplurality of carboxylate groups, preferably at least 3 carboxylates.Carboxylate builders can be formulated in acid, partially neutral,neutral or overbased form. When in salt form, alkali metals, such assodium, potassium, and lithium, or alkanolammonium salts are preferred.Polycarboxylate builders include the ether polycarboxylates, such asoxydisuccinate, see Berg, U.S. Pat. No. 3,128,287, Apr. 7, 1964, andLamberti et al, U.S. Pat. No. 3,635,830, Jan. 18, 1972; "TMS/TDS"builders of U.S. Pat. No. 4,663,071, Bush et al, May 5, 1987; and otherether carboxylates including cyclic and alicyclic compounds, such asthose described in U.S. Pat. Nos. 3,923,679; 3,835,163; 4,158,635;4,120,874 and 4,102,903.

Other suitable builders are the ether hydroxypolycarboxylates,copolymers of maleic anhydride with ethylene or vinyl methyl ether; 1,3, 5-trihydroxy benzene-2, 4, 6-trisulphonic acid;carboxymethyloxysuccinic acid; the various alkali metal, ammonium andsubstituted ammonium salts of polyacetic acids such as ethylenediaminetetraacetic acid and nitrilotriacetic acid; as well as mellitic acid,succinic acid, polymaleic acid, benzene 1,3,5-tricarboxylic acid,carboxy-methyloxysuccinic acid, and soluble salts thereof.

Citrates, e.g., citric acid and soluble salts thereof are importantcarboxylate builders e.g., for heavy duty liquid detergents, due toavailability from renewable resources and biodegradability. Citrates canalso be used in granular compositions, especially in combination withzeolite and/or layered silicates. Oxydisuccinates are also especiallyuseful in such compositions and combinations.

Where permitted, and especially in the formulation of bars used forhand-laundering operations, alkali metal phosphates such as sodiumtripolyphosphates, sodium pyrophosphate and sodium orthophosphate can beused. Phosphonate builders such as ethane-1-hydroxy-1,1-diphosphonateand other known phosphonates, e.g., those of U.S. Pat. Nos. 3,159,581;3,213,030; 3,422,021; 3,400,148 and 3,422,137 can also be used and mayhave desirable antiscaling properties.

Certain detersive surfactants or their short-chain homologs also have abuilder action. For unambiguous formula accounting purposes, when theyhave surfactant capability, these materials are summed up as detersivesurfactants. Preferred types for builder functionality are illustratedby: 3,3-dicarboxy-4-oxa-1,6-hexanedioates and the related compoundsdisclosed in U.S. Pat. No. 4,566,984, Bush, Jan. 28, 1986. Succinic acidbuilders include the C₅ -C₂₀ alkyl and alkenyl succinic acids and saltsthereof Succinate builders also include: laurylsuccinate,myristylsuccinate, palmitylsuccinate, 2-dodecenylsuccinate (preferred),2-pentadecenylsuccinate, and the like. Lauryl-succinates are describedin European Patent Application 86200690.5/0,200,263, published Nov. 5,1986. Fatty acids, e.g., C₁₂ -C₁₈ monocarboxylic acids, can also beincorporated into the compositions as surfactant/builder materials aloneor in combination with the aforementioned builders, especially citrateand/or the succinate builders, to provide additional builder activity.Other suitable polycarboxylates are disclosed in U.S. Pat. No.4,144,226, Crutchfield et al, Mar. 13, 1979 and in U.S. Pat. No.3,308,067, Diehl, Mar. 7, 1967. See also Diehl, U.S. Pat. No. 3,723,322.

Other types of inorganic builder materials which can be used have theformula (M_(x))_(i) Ca_(y) (CO₃)_(z) wherein x and i are integers from 1to 15, y is an integer from 1 to 10, z is an integer from 2 to 25, M_(i)are cations, at least one of which is a water-soluble, and the equationΣ_(i=1-15) (x_(i) multiplied by the valence of M_(i))+2y=2z is satisfiedsuch that the formula has a neutral or "balanced" charge. These buildersare referred to herein as "Mineral Builders". Waters of hydration oranions other than carbonate may be added provided that the overallcharge is balanced or neutral. The charge or valence effects of suchanions should be added to the right side of the above equation.Preferably, there is present a water-soluble cation selected from thegroup consisting of hydrogen, water-soluble metals, hydrogen, boron,ammonium, silicon, and mixtures thereof, more preferably, sodium,potassium, hydrogen, lithium, ammonium and mixtures thereof, sodium andpotassium being highly preferred. Nonlimiting examples of noncarbonateanions include those selected from the group consisting of chloride,sulfate, fluoride, oxygen, hydroxide, silicon dioxide, chromate,nitrate, borate and mixtures thereof Preferred builders of this type intheir simplest forms are selected from the group consisting of Na₂Ca(CO₃)₂, K₂ Ca(CO₃)₂, Na₂ Ca₂ (CO₃)₃, NaKCa(CO₃)₂, NaKCa₂ (CO₃)₃, K₂Ca₂ (CO₃)₃, and combinations thereof. An especially preferred materialfor the builder described herein is Na₂ Ca(CO₃)₂ in any of itscrystalline modifications. Suitable builders of the above-defined typeare further illustrated by, and include, the natural or synthetic formsof any one or combinations of the following minerals: Afghanite,Andersonite, AshcroftineY, Beyerite, Borcarite, Burbankite, Butschliite,Cancrinite, Carbocernaite, Carletonite, Davyne, DonnayiteY,Fairchildite, Ferrisurite, Franzinite, Gaudefroyite, Gaylussite,Girvasite, Gregoryite, Jouravskite, KamphaugiteY, Kettnerite,Khanneshite, LepersonniteGd, Liottite, MckelveyiteY, Microsommite,Mroseite, Natrofairchildite, Nyerereite, RemonditeCe, Sacrofanite,Schrockingerite, Shortite, Surite, Tunisite, Tuscanite, Tyrolite,Vishnevite, and Zemkorite. Preferred mineral forms include Nyererite,Fairchildite and Shortite.

Polymeric Soil Release Agent--Known polymeric soil release agents,hereinafter "SRA" or "SRA's", can optionally be employed in the presentdetergent compositions. If utilized, SRA's will generally comprise from0.01% to 10.0%, typically from 0.1% to 5%, preferably from 0.2% to 3.0%by weight, of the composition.

Preferred SRA's typically have hydrophilic segments to hydrophilize thesurface of hydrophobic fibers such as polyester and nylon, andhydrophobic segments to deposit upon hydrophobic fibers and remainadhered thereto through completion of washing and rinsing cycles therebyserving as an anchor for the hydrophilic segments. This can enablestains occurring subsequent to treatment with SRA to be more easilycleaned in later washing procedures.

SRA's can include a variety of charged, e.g., anionic or even cationic(see U.S. Pat. No. 4,956,447), as well as noncharged monomer units andstructures may be linear, branched or even star-shaped. They may includecapping moieties which are especially effective in controlling molecularweight or altering the physical or surface-active properties. Structuresand charge distributions may be tailored for application to differentfiber or textile types and for varied detergent or detergent additiveproducts.

Preferred SRA's include oligomeric terephthalate esters, typicallyprepared by processes involving at least onetransesterification/oligomerization, often with a metal catalyst such asa titanium(IV) alkoxide. Such esters may be made using additionalmonomers capable of being incorporated into the ester structure throughone, two, three, four or more positions, without of course forming adensely crosslinked overall structure.

Suitable SRA's include: a sulfonated product of a substantially linearester oligomer comprised of an oligomeric ester backbone ofterephthaloyl and oxyalkyleneoxy repeat units and allyl-derivedsulfonated terminal moieties covalently attached to the backbone, forexample as described in U.S. Pat. No. 4,968,451, Nov. 6, 1990 to J. J.Scheibel and E. P. Gosselink: such ester oligomers can be prepared by(a) ethoxylating allyl alcohol, (b) reacting the product of (a) withdimethyl terephthalate ("DMT") and 1,2-propylene glycol ("PG") in atwo-stage transesterification/oligomerization procedure and (c) reactingthe product of (b) with sodium metabisulfite in water; the nonionicend-capped 1,2-propylene/polyoxyethylene terephthalate polyesters ofU.S. Pat. No. 4,711,730, Dec. 8, 1987 to Gosselink et al, for examplethose produced by transesterification/oligomerization ofpoly(ethyleneglycol) methyl ether, DMT, PG and poly(ethyleneglycol)("PEG"); the partly- and fully- anionic-end-capped oligomeric esters ofU.S. Pat. No. 4,721,580, Jan. 26, 1988 to Gosselink, such as oligomersfrom ethylene glycol ("EG"), PG, DMT andNa-3,6-dioxa-8-hydroxyoctanesulfonate; the nonionic-capped blockpolyester oligomeric compounds of U.S. Pat. No. 4,702,857, Oct. 27, 1987to Gosselink, for example produced from DMT, Me-capped PEG and EG and/orPG, or a combination of DMT, EG and/or PG, Me-capped PEG andNa-dimethyl-5-sulfoisophthalate; and the anionic, especially sulfoaroyl,end-capped terephthalate esters of U.S. Pat. No. 4,877,896, Oct. 31,1989 to Maldonado, Gosselink et al, the latter being typical of SRA'suseful in both laundry and fabric conditioning products, an examplebeing an ester composition made from m-sulfobenzoic acid monosodiumsalt, PG and DMT optionally but preferably further comprising added PEG,e.g., PEG 3400.

SRA's also include simple copolymeric blocks of ethylene terephthalateor propylene terephthalate with polyethylene oxide or polypropyleneoxide terephthalate, see U.S. Pat. No. 3,959,230 to Hays, May 25, 1976and U.S. Pat. No. 3,893,929 to Basadur, Jul. 8, 1975; cellulosicderivatives such as the hydroxyether cellulosic polymers available asMETHOCEL from Dow; and the C₁ -C₄ alkylcelluloses and C₄ hydroxyalkylcelluloses; see U.S. Pat. No. 4,000,093, Dec. 28, 1976 to Nicol, et al.Suitable SRA's characterised by poly(vinyl ester) hydrophobe segmentsinclude graft copolymers of poly(vinyl ester), e.g., C₁ -C₆ vinylesters, preferably poly(vinyl acetate), grafted onto polyalkylene oxidebackbones. See European Patent Application 0 219 048, published Apr. 22,1987 by Kud, et al. Commercially available examples include SOKALANSRA's such as SOKALAN HP-22, available from BASF, Germany. Other SRA'sare polyesters with repeat units containing 10-15% by weight of ethyleneterephthalate together with 90-80% by weight of polyoxyethyleneterephthalate, derived from a polyoxyethylene glycol of averagemolecular weight 300-5,000. Commercial examples include ZELCON 5126 fromDupont and MILEASE T from ICI.

Another preferred SRA is an oligomer having empirical formula (CAP)₂(EG/PG)₅ (T)₅ (SIP)₁ which comprises terephthaloyl (T),sulfoisophthaloyl (SIP), oxyethyleneoxy and oxy-1,2-propylene (EG/PG)units and which is preferably terminated with end-caps (CAP), preferablymodified isethionates, as in an oligomer comprising onesulfoisophthaloyl unit, 5 terephthaloyl units, oxyethyleneoxy andoxy-1,2-propyleneoxy units in a defined ratio, preferably about 0.5:1 toabout 10:1, and two end-cap units derived from sodium2-(2-hydroxyethoxy)-ethanesulfonate. Said SRA preferably furthercomprises from 0.5% to 20%, by weight of the oligomer, of acrystallinity-reducing stabiliser, for example an anionic surfactantsuch as linear sodium dodecylbenzenesulfonate or a member selected fromxylene-, cumene-, and toluene-sulfonates or mixtures thereof, thesestabilizers or modifiers being introduced into the synthesis pot, all astaught in U.S. Pat. No. 5,415,807, Gosselink, Pan, Kellett and Hall,issued May 16, 1995. Suitable monomers for the above SRA include Na2-(2-hydroxyethoxy)-ethanesulfonate, DMT, Na-dimethyl5-sulfoisophthalate, EG and PG.

Yet another group of preferred SRA's are oligomeric esters comprising:(1) a backbone comprising (a) at least one unit selected from the groupconsisting of dihydroxysulfonates, polyhydroxy sulfonates, a unit whichis at least trifunctional whereby ester linkages are formed resulting ina branched oligomer backbone, and combinations thereof, (b) at least oneunit which is a terephthaloyl moiety; and (c) at least one unsulfonatedunit which is a 1,2-oxyalkyleneoxy moiety; and (2) one or more cappingunits selected from nonionic capping units, anionic capping units suchas alkoxylated, preferably ethoxylated, isethionates, alkoxylatedpropanesulfonates, alkoxylated propanedisulfonates, alkoxylatedphenolsulfonates, sulfoaroyl derivatives and mixtures thereof Preferredof such esters are those of empirical formula:

    {(CAP)×(EG/PG)y'(DEG)y"(PEG)y'"(T)z(SIP)z'(SEG)q(B)m}

wherein CAP, EG/PG, PEG, T and SIP are as defined hereinabove, (DEG)represents di(oxyethylene)oxy units; (SEG) represents units derived fromthe sulfoethyl ether of glycerin and related moiety units; (B)represents branching units which are at least trifunctional wherebyester linkages are formed resulting in a branched oligomer backbone; xis from about 1 to about 12; y' is from about 0.5 to about 25; y" isfrom 0 to about 12; y'" is from 0 to about 10; y'+y"+y'" totals fromabout 0.5 to about 25; z is from about 1.5 to about 25; z' is from 0 toabout 12; z+z' totals from about 1.5 to about 25; q is from about 0.05to about 12, m is from about 0.01 to about 10; and x, y', y", y'", z,z', q and m represent the average number of moles of the correspondingunits per mole of said ester and said ester has a molecular weightranging from about 500 to about 5,000.

Preferred SEG and CAP monomers for the above esters includeNa-2-(2-,3-dihydroxypropoxy)ethanesulfonate ("SEG"),Na-2-{2-(2-hydroxyethoxy) ethoxy} ethanesulfonate ("SE3") and itshomologs and mixtures thereof and the products of ethoxylating andsulfonating allyl alcohol. Preferred SRA esters in this class includethe product of transesterifying and oligomerizing sodium2-{2-(2-hydroxyethoxy)ethoxy}ethanesulfonate and/or sodium2-[2-{2-(2-hydroxyethoxy)-ethoxy}ethoxy]ethanesulfonate, DMT, sodium2-(2,3-dihydroxypropoxy) ethane sulfonate, EG, and PG using anappropriate Ti(IV) catalyst and can be designated as(CAP)2(T)5(EG/PG)1.4(SEG)2.5(B)0.13 wherein CAP is (Na+--O₃ S[CH₂ CH₂O]3.5)- and B is a unit from glycerin and the mole ratio EG/PG is about1.7:1 as measured by conventional gas chromatography after completehydrolysis.

Additional classes of SRA's include (I) nonionic terephthalates usingdiisocyanate coupling agents to link up polymeric ester structures, seeU.S. Pat. No. 4,201,824, Violland et al. and U.S. Pat. No. 4,240,918Lagasse et al; (II) SRA's with carboxylate terminal groups made byadding trimellitic anhydride to known SRA's to convert terminal hydroxylgroups to trimellitate esters. With a proper selection of catalyst, thetrimellitic anhydride forms linkages to the terminals of the polymerthrough an ester of the isolated carboxylic acid of trimelliticanhydride rather than by opening of the anhydride linkage. Eithernonionic or anionic SRA's may be used as starting materials as long asthey have hydroxyl terminal groups which may be esterified. See U.S.Pat. No. 4,525,524 Tung et al.; (III) anionic terephthalate-based SRA'sof the urethane-linked variety, see U.S. Pat. No. 4,201,824, Violland etal; (IV) poly(vinyl caprolactam) and related co-polymers with monomerssuch as vinyl pyrrolidone and/or dimethylaminoethyl methacrylate,including both nonionic and cationic polymers, see U.S. Pat. No.4,579,681, Ruppert et al.; (V) graft copolymers, in addition to theSOKALAN types from BASF made, by grafting acrylic monomers on tosulfonated polyesters; these SRA's assertedly have soil release andanti-redeposition activity similar to known cellulose ethers: see EP279,134 A, 1988, to Rhone-Poulenc Chemie; (VI) grafts of vinyl monomerssuch as acrylic acid and vinyl acetate on to proteins such as caseins,see EP 457,205 A to BASF (1991); (VII) polyester-polyamide SRA'sprepared by condensing adipic acid, caprolactam, and polyethyleneglycol, especially for treating polyamide fabrics, see Bevan et al, DE2,335,044 to Unilever N. V., 1974. Other useful SRA's are described inU.S. Pat. Nos. 4,240,918, 4,787,989, 4,525,524 and 4,877,896.

Clay Soil Removal/Anti-redeposition Agents--The compositions of thepresent invention can also optionally contain water-soluble ethoxylatedamines having clay soil removal and antiredeposition properties.Granular detergent compositions which contain these compounds typicallycontain from about 0.01% to about 10.0% by weight of the water-solubleethoxylates amines; liquid detergent compositions typically containabout 0.01% to about 5%.

The most preferred soil release and anti-redeposition agent isethoxylated tetraethylenepentamine. Exemplary ethoxylated amines arefurther described in U.S. Pat. No. 4,597,898, VanderMeer, issued Jul. 1,1986. Another group of preferred clay soil removal-antiredepositionagents are the cationic compounds disclosed in European PatentApplication 111,965, Oh and Gosselink, published Jun. 27, 1984. Otherclay soil removal/antiredeposition agents which can be used include theethoxylated amine polymers disclosed in European Patent Application111,984, Gosselink, published Jun. 27, 1984; the zwitterionic polymersdisclosed in European Patent Application 112,592, Gosselink, publishedJul. 4, 1984; and the amine oxides disclosed in U.S. Pat. No. 4,548,744,Connor, issued Oct. 22, 1985. Other clay soil removal and/or antiredeposition agents known in the art can also be utilized in thecompositions herein. See U.S. Pat. No. 4,891,160, VanderMeer, issuedJan. 2, 1990 and WO 95/32272, published Nov. 30, 1995. Another type ofpreferred antiredeposition agent includes the carboxy methyl cellulose(CMC) materials. These materials are well known in the art.

Polymeric Dispersing Agents--Polymeric dispersing agents canadvantageously be utilized at levels from about 0.1% to about 7%, byweight, in the compositions herein, especially in the presence ofzeolite and/or layered silicate builders. Suitable polymeric dispersingagents include polymeric polycarboxylates and polyethylene glycols,although others known in the art can also be used. It is believed,though it is not intended to be limited by theory, that polymericdispersing agents enhance overall detergent builder performance, whenused in combination with other builders (including lower molecularweight polycarboxylates) by crystal growth inhibition, particulate soilrelease peptization, and anti-redeposition.

Polymeric polycarboxylate materials can be prepared by polymerizing orcopolymerizing suitable unsaturated monomers, preferably in their acidform. Unsaturated monomeric acids that can be polymerized to formsuitable polymeric polycarboxylates include acrylic acid, maleic acid(or maleic anhydride), fumaric acid, itaconic acid, aconitic acid,mesaconic acid, citraconic acid and methylenemalonic acid. The presencein the polymeric polycarboxylates herein or monomeric segments,containing no carboxylate radicals such as vinylmethyl ether, styrene,ethylene, etc. is suitable provided that such segments do not constitutemore than about 40% by weight.

Particularly suitable polymeric polycarboxylates can be derived fromacrylic acid. Such acrylic acid-based polymers which are useful hereinare the water-soluble salts of polymerized acrylic acid. The averagemolecular weight of such polymers in the acid form preferably rangesfrom about 2,000 to 10,000, more preferably from about 4,000 to 7,000and most preferably from about 4,000 to 5,000. Water-soluble salts ofsuch acrylic acid polymers can include, for example, the alkali metal,ammonium and substituted ammonium salts. Soluble polymers of this typeare known materials. Use of polyacrylates of this type in detergentcompositions has been disclosed, for example, in Diehl, U.S. Pat. No.3,308,067, issued Mar. 7, 1967.

Acrylic/maleic-based copolymers may also be used as a preferredcomponent of the dispersing/anti-redeposition agent. Such materialsinclude the water-soluble salts of copolymers of acrylic acid and maleicacid. The average molecular weight of such copolymers in the acid formpreferably ranges from about 2,000 to 100,000, more preferably fromabout 5,000 to 75,000, most preferably from about 7,000 to 65,000. Theratio of acrylate to maleate segments in such copolymers will generallyrange from about 30:1 to about 1:1, more preferably from about 10:1 to2:1. Water-soluble salts of such acrylic acid/maleic acid copolymers caninclude, for example, the alkali metal, ammonium and substitutedammonium salts. Soluble acrylate/maleate copolymers of this type areknown materials which are described in European Patent Application No.66915, published Dec. 15, 1982, as well as in EP 193,360, published Sep.3, 1986, which also describes such polymers comprisinghydroxypropylacrylate. Still other useful dispersing agents include themaleic/acrylic/vinyl alcohol terpolymers. Such materials are alsodisclosed in EP 193,360, including, for example, the 45/45/10 terpolymerof acrylic/maleic/vinyl alcohol.

Another polymeric material which can be included is polyethylene glycol(PEG). PEG can exhibit dispersing agent performance as well as act as aclay soil removal-antiredeposition agent. Typical molecular weightranges for these purposes range from about 500 to about 100,000,preferably from about 1,000 to about 50,000, more preferably from about1,500 to about 10,000.

Polyaspartate and polyglutamate dispersing agents may also be used,especially in conjunction with zeolite builders. Dispersing agents suchas polyaspartate preferably have a molecular weight (avg.) of about10,000.

Brightener--Any optical brighteners or other brightening or whiteningagents known in the art can be incorporated at levels typically fromabout 0.01% to about 1.2%, by weight, into the detergent compositionsherein. Commercial optical brighteners which may be useful in thepresent invention can be classified into subgroups, which include, butare not necessarily limited to, derivatives of stilbene, pyrazoline,coumarin, carboxylic acid, methinecyanines,dibenzothiophene-5,5-dioxide, azoles, 5- and 6-membered-ringheterocycles, and other miscellaneous agents. Examples of suchbrighteners are disclosed in "The Production and Application ofFluorescent Brightening Agents", M. Zahradnik, Published by John Wiley &Sons, New York (1982).

Specific examples of optical brighteners which are useful in the presentcompositions are those identified in U.S. Pat. No. 4,790,856, issued toWixon on Dec. 13, 1988. These brighteners include the PHORWHITE seriesof brighteners from Verona. Other brighteners disclosed in thisreference include: Tinopal UNPA, Tinopal CBS and Tinopal 5BM; availablefrom Ciba-Geigy; Artic White CC and Artic White CWD, the2-(4-styryl-phenyl)-2H-naptho[1,2-d]triazoles;4,4'-bis-(1,2,3-triazol-2-yl)-stilbenes; 4,4'-bis(styryl)bisphenyls; andthe amino-coumarins. Specific examples of these brighteners include4-methyl-7-diethyl-amino coumarin; 1,2-bis(benzimidazol-2-yl)ethylene;1,3-diphenyl-pyrazolines; 2,5-bis(benzoxazol-2-yl)thiophene;2-styryl-naptho[1,2-d]oxazole; and2-(stilben-4-yl)-2H-naphtho[1,2-d]triazole. See also U.S. Pat. No.3,646,015, issued Feb. 29, 1972 to Hamilton.

Dye Transfer Inhibiting Agents--The compositions of the presentinvention may also include one or more materials effective forinhibiting the transfer of dyes from one fabric to another during thecleaning process. Generally, such dye transfer inhibiting agents includepolyvinyl pyrrolidone polymers, polyamine N-oxide polymers, copolymersof N-vinylpyrrolidone and N-vinylimidazole, manganese phthalocyanine,peroxidases, and mixtures thereof. If used, these agents typicallycomprise from about 0.01% to about 10% by weight of the composition,preferably from about 0.01% to about 5%, and more preferably from about0.05% to about 2%.

More specifically, the polyamine N-oxide polymers preferred for useherein contain units having the following structural formula: R--A_(x)--P; wherein P is a polymerizable unit to which an N--O group can beattached or the N--O group can form part of the polymerizable unit orthe N--O group can be attached to both units; A is one of the followingstructures: --NC(O)--, --C(O)O--, --S--, --O--, --N═; x is 0 or 1; and Ris aliphatic, ethoxylated aliphatics, aromatics, heterocyclic oralicyclic groups or any combination thereof to which the nitrogen of theN--O group can be attached or the N--O group is part of these groups.Preferred polyamine N-oxides are those wherein R is a heterocyclic groupsuch as pyridine, pyrrole, imidazole, pyrrolidine, piperidine andderivatives thereof.

The N--O group can be represented by the following general structures:##STR44## wherein R₁, R₂, R₃ are aliphatic, aromatic, heterocyclic oralicyclic groups or combinations thereof; x, y and z are 0 or 1; and thenitrogen of the N--O group can be attached or form part of any of theaforementioned groups. The amine oxide unit of the polyamine N-oxideshas a pKa <10, preferably pKa <7, more preferred pKa <6.

Any polymer backbone can be used as long as the amine oxide polymerformed is water-soluble and has dye transfer inhibiting properties.Examples of suitable polymeric backbones are polyvinyls, polyalkylenes,polyesters, polyethers, polyamide, polyimides, polyacrylates andmixtures thereof These polymers include random or block copolymers whereone monomer type is an amine N-oxide and the other monomer type is anN-oxide. The amine N-oxide polymers typically have a ratio of amine tothe amine N-oxide of 10:1 to 1:1,000,000. However, the number of amineoxide groups present in the polyamine oxide polymer can be varied byappropriate copolymerization or by an appropriate degree of N-oxidation.The polyamine oxides can be obtained in almost any degree ofpolymerization. Typically, the average molecular weight is within therange of 500 to 1,000,000; more preferred 1,000 to 500,000; mostpreferred 5,000 to 100,000. This preferred class of materials can bereferred to as "PVNO".

The most preferred polyamine N-oxide useful in the detergentcompositions herein is poly(4-vinylpyridine-N-oxide) which as an averagemolecular weight of about 50,000 and an amine to amine N-oxide ratio ofabout 1:4.

Copolymers of N-vinylpyrrolidone and N-vinylimidazole polymers (referredto as a class as "PVPVI") are also preferred for use herein. Preferablythe PVPVI has an average molecular weight range from 5,000 to 1,000,000,more preferably from 5,000 to 200,000, and most preferably from 10,000to 20,000. (The average molecular weight range is determined by lightscattering as described in Barth, et al., Chemical Analysis, Vol 113."Modem Methods of Polymer Characterization", the disclosures of whichare incorporated herein by reference.) The PVPVI copolymers typicallyhave a molar ratio of N-vinylimidazole to N-vinylpyrrolidone from 1:1 to0.2:1, more preferably from 0.8:1 to 0.3:1, most preferably from 0.6:1to 0.4:1. These copolymers can be either linear or branched.

The present invention compositions also may employ apolyvinylpyrrolidone ("PVP") having an average molecular weight of fromabout 5,000 to about 400,000, preferably from about 5,000 to about200,000, and more preferably from about 5,000 to about 50,000. PVP's areknown to persons skilled in the detergent field; see, for example,EP-A-262,897 and EP-A-256,696, incorporated herein by reference.Compositions containing PVP can also contain polyethylene glycol ("PEG")having an average molecular weight from about 500 to about 100,000,preferably from about 1,000 to about 10,000. Preferably, the ratio ofPEG to PVP on a ppm basis delivered in wash solutions is from about 2:1to about 50:1, and more preferably from about 3:1 to about 10:1.

The detergent compositions herein may also optionally contain from about0.005% to 5% by weight of certain types of hydrophilic opticalbrighteners which also provide a dye transfer inhibition action. Ifused, the compositions herein will preferably comprise from about 0.01%to 1% by weight of such optical brighteners.

The hydrophilic optical brighteners useful in the present invention arethose having the structural formula: ##STR45## wherein R.sup. isselected from anilino, N-2-bis-hydroxyethyl and NH-2-hydroxyethyl; R₂ isselected from N-2-bis-hydroxyethyl, N-2-hydroxyethyl-N-methylamino,morphilino, chloro and amino; and M is a salt-forming cation such assodium or potassium.

When in the above formula, R₁ is anilino, R₂ is N-2-bis-hydroxyethyl andM is a cation such as sodium, the brightener is4,4',-bis[(4-anilino-6-(N-2-bis-hydroxyethyl)-s-triazine-2-yl)amino]-2,2'-stilbenedisulfonicacid and disodium salt. This particular brightener species iscommercially marketed under the tradename Tinopal-UNPA-GX by Ciba-GeigyCorporation. Tinopal-UNPA-GX is the preferred hydrophilic opticalbrightener useful in the detergent compositions herein.

When in the above formula, R₁ is anilino, R₂ isN-2-hydroxyethyl-N-2-methylamino and M is a cation such as sodium, thebrightener is4,4'-bis[(4-anilino-6-(N-2-hydroxyethyl-N-methylamino)-s-triazine-2-yl)amino]2,2'-stilbenedisulfonicacid disodium salt. This particular brightener species is commerciallymarketed under the tradename Tinopal 5BM-GX by Ciba-Geigy Corporation.

When in the above formula, R.sup. is anilino, R₂ is morphilino and M isa cation such as sodium, the brightener is4,4'-bis[(4-anilino-6-morphilino-s-triazine-2-yl)amino]2,2'-stilbenedisulfonicacid, sodium salt. This particular brightener species is commerciallymarketed under the tradename Tinopal AMS-GX by Ciba Geigy Corporation.

The specific optical brightener species selected for use in the presentinvention provide especially effective dye transfer inhibitionperformance benefits when used in combination with the selectedpolymeric dye transfer inhibiting agents hereinbefore described. Thecombination of such selected polymeric materials (e.g., PVNO and/orPVPVI) with such selected optical brighteners (e.g., Tinopal UNPA-GX,Tinopal 5BM-GX and/or Tinopal AMS-GX) provides significantly better dyetransfer inhibition in aqueous wash solutions than does either of thesetwo detergent composition components when used alone. Without beingbound by theory, it is believed that such brighteners work this waybecause they have high affinity for fabrics in the wash solution andtherefore deposit relatively quick on these fabrics. The extent to whichbrighteners deposit on fabrics in the wash solution can be defined by aparameter called the "exhaustion coefficient". The exhaustioncoefficient is in general as the ratio of a) the brightener materialdeposited on fabric to b) the initial brightener concentration in thewash liquor. Brighteners with relatively high exhaustion coefficientsare the most suitable for inhibiting dye transfer in the context of thepresent invention.

Of course, it will be appreciated that other, conventional opticalbrightener types of compounds can optionally be used in the presentcompositions to provide conventional fabric "brightness" benefits,rather than a true dye transfer inhibiting effect. Such usage isconventional and well-known to detergent formulations.

Chelating Agents--The detergent compositions herein may also optionallycontain one or more iron and/or manganese chelating agents. Suchchelating agents can be selected from the group consisting of aminocarboxylates, amino phosphonates, polyfunctionally-substituted aromaticchelating agents and mixtures therein, all as hereinafter defined.Without intending to be bound by theory, it is believed that the benefitof these materials is due in part to their exceptional ability to removeiron and manganese ions from washing solutions by formation of solublechelates.

Amino carboxylates useful as optional chelating agents includeethylenediaminetetracetates, N-hydroxyethylethylenediaminetriacetates,nitrilotriacetates, ethylenediamine tetraproprionates,triethylenetetraaminehexacetates, diethylenetriaminepentaacetates, andethanoldiglycines, alkali metal, ammonium, and substituted ammoniumsalts therein and mixtures therein.

Amino phosphonates are also suitable for use as chelating agents in thecompositions of the invention when at lease low levels of totalphosphorus are permitted in detergent compositions, and includeethylenediaminetetrakis (methylenephosphonates) as DEQUEST. Preferred,these amino phosphonates to not contain alkyl or alkenyl groups withmore than about 6 carbon atoms.

Polyfunctionally-substituted aromatic chelating agents are also usefulin the compositions herein. See U.S. Pat. No. 3,812,044, issued May 21,1974, to Connor et al. Preferred compounds of this type in acid form aredihydroxydisulfobenzenes such as 1,2-dihydroxy-3,5-disulfobenzene.

A preferred biodegradable chelator for use herein is ethylenediaminedisuccinate ("EDDS"), especially the [S,S] isomer as described in U.S.Pat. No. 4,704,233, Nov. 3, 1987, to Hartman and Perkins.

The compositions herein may also contain water-soluble methyl glycinediacetic acid (MGDA) salts (or acid form) as a chelant or co-builderuseful with, for example, insoluble builders such as zeolites, layeredsilicates and the like.

If utilized, these chelating agents will generally comprise from about0.1% to about 15% by weight of the detergent compositions herein. Morepreferably, if utilized, the chelating agents will comprise from about0.1% to about 3.0% by weight of such compositions.

Suds Suppressors--Compounds for reducing or suppressing the formation ofsuds can be incorporated into the compositions of the present invention.Suds suppression can be of particular importance in the so-called "highconcentration cleaning process" as described in U.S. Pat. Nos. 4,489,455and 4,489,574 and in front-loading European-style washing machines.

A wide variety of materials may be used as suds suppressors, and sudssuppressors are well known to those skilled in the art. See, forexample, Kirk Othmer Encyclopedia of Chemical Technology, Third Edition,Volume 7, pages 430-447 (John Wiley & Sons, Inc., 1979). One category ofsuds suppressor of particular interest encompasses monocarboxylic fattyacid and soluble salts therein. See U.S. Pat. No. 2,954,347, issued Sep.27, 1960 to Wayne St. John. The monocarboxylic fatty acids and saltsthereof used as suds suppressor typically have hydrocarbyl chains of 10to about 24 carbon atoms, preferably 12 to 18 carbon atoms. Suitablesalts include the alkali metal salts such as sodium, potassium, andlithium salts, and ammonium and alkanolammonium salts.

The detergent compositions herein may also contain non-surfactant sudssuppressors. These include, for example: high molecular weighthydrocarbons such as paraffin, fatty acid esters (e.g., fatty acidtriglycerides), fatty acid esters of monovalent alcohols, aliphatic C₁₈-C₄₀ ketones (e.g., stearone), etc. Other suds inhibitors includeN-alkylated amino triazines such as tri- to hexa-alkylmelamines or di-to tetra-alkyldiamine chlortriazines formed as products of cyanuricchloride with two or three moles of a primary or secondary aminecontaining 1 to 24 carbon atoms, propylene oxide, and monostearylphosphates such as monostearyl alcohol phosphate ester and monostearyldi-alkali metal (e.g., K, Na, and Li) phosphates and phosphate esters.The hydrocarbons such as paraffin and haloparaffin can be utilized inliquid form. The liquid hydrocarbons will be liquid at room temperatureand atmospheric pressure, and will have a pour point in the range ofabout -40° C. and about 50° C., and a minimum boiling point not lessthan about 110° C. (atmospheric pressure). It is also known to utilizewaxy hydrocarbons, preferably having a melting point below about 100° C.The hydrocarbons constitute a preferred category of suds suppressor fordetergent compositions. Hydrocarbon suds suppressors are described, forexample, in U.S. Pat. No. 4,265,779, issued May 5, 1981 to Gandolfo etal. The hydrocarbons, thus, include aliphatic, alicyclic, aromatic, andheterocyclic saturated or unsaturated hydrocarbons having from about 12to about 70 carbon atoms. The term "paraffin," as used in this sudssuppressor discussion, is intended to include mixtures of true paraffinsand cyclic hydrocarbons.

Another preferred category of non-surfactant suds suppressors comprisessilicone suds suppressors. This category includes the use ofpolyorganosiloxane oils, such as polydimethylsiloxane, dispersions oremulsions of polyorganosiloxane oils or resins, and combinations ofpolyorganosiloxane with silica particles wherein the polyorganosiloxaneis chemisorbed or fused onto the silica. Silicone suds suppressors arewell known in the art and are, for example, disclosed in U.S. Pat. No.4,265,779, issued May 5, 1981 to Gandolfo et al and European PatentApplication No. 89307851.9, published Feb. 7, 1990, by Starch, M. S.

Other silicone suds suppressors are disclosed in U.S. Pat. No. 3,455,839which relates to compositions and processes for defoaming aqueoussolutions by incorporating therein small amounts of polydimethylsiloxanefluids.

Mixtures of silicone and silanated silica are described, for instance,in German Patent Application DOS 2,124,526. Silicone defoamers and sudscontrolling agents in granular detergent compositions are disclosed inU.S. Pat. No. 3,933,672, Bartolotta et al, and in U.S. Pat. No.4,652,392, Baginski et al, issued Mar. 24, 1987.

An exemplary silicone based suds suppressor for use herein is a sudssuppressing amount of a suds controlling agent consisting essentiallyof:

(i) polydimethylsiloxane fluid having a viscosity of from about 20 cs.to about 1,500 cs. at 25° C.;

(ii) from about 5 to about 50 parts per 100 parts by weight of (i) ofsiloxane resin composed of (CH₃)₃ SiO_(1/2) units of SiO₂ units in aratio of from (CH₃)₃ SiO_(1/2) units and to SiO₂ units of from about0.6:1 to about 1.2:1; and

(iii) from about 1 to about 20 parts per 100 parts by weight of (i) of asolid silica gel.

In the preferred silicone suds suppressor used herein, the solvent for acontinuous phase is made up of certain polyethylene glycols orpolyethylene-polypropylene glycol copolymers or mixtures thereof(preferred), or polypropylene glycol. The primary silicone sudssuppressor is branched/crosslinked and preferably not linear.

To illustrate this point further, typical liquid laundry detergentcompositions with controlled suds will optionally comprise from about0.001 to about 1, preferably from about 0.01 to about 0.7, mostpreferably from about 0.05 to about 0.5, weight % of said silicone udssuppressor, which comprises (1) a nonaqueous emulsion of a primaryantifoam agent which is a mixture of (a) a polyorganosiloxane, (b) aresinous siloxane or a silicone resin-producing silicone compound, (c) afinely divided filler material, and (d) a catalyst to promote thereaction of mixture components (a), (b) and (c), to form silanolates;(2) at least one nonionic silicone surfactant; and (3) polyethyleneglycol or a copolymer of polyethylene-polypropylene glycol having asolubility in water at room temperature of more than about 2 weight %;and without polypropylene glycol. Similar amounts can be used ingranular compositions, gels, etc. See also U.S. Pat. No. 4,978,471,Starch, issued Dec. 18, 1990, and U.S. Pat. No. 4,983,316, Starch,issued Jan. 8, 1991, U.S. Pat. No. 5,288,431, Huber et al., issued Feb.22, 1994, and U.S. Pat. Nos. 4,639,489 and 4,749,740, Aizawa et al atcolumn 1, line 46 through column 4, line 35.

The silicone suds suppressor herein preferably comprises polyethyleneglycol and a copolymer of polyethylene glycol/polypropylene glycol, allhaving an average molecular weight of less than about 1,000, preferablybetween about 100 and 800. The polyethylene glycol andpolyethylene/polypropylene copolymers herein have a solubility in waterat room temperature of more than about 2 weight %, preferably more thanabout 5 weight %.

The preferred solvent herein is polyethylene glycol having an averagemolecular weight of less than about 1,000, more preferably between about100 and 800, most preferably between 200 and 400, and a copolymer ofpolyethylene glycol/polypropylene glycol, preferably PPG 200/PEG 300.Preferred is a weight ratio of between about 1:1 and 1:10, mostpreferably between 1:3 and 1:6, of polyethylene glycol:copolymer ofpolyethylene-polypropylene glycol.

The preferred silicone suds suppressors used herein do not containpolypropylene glycol, particularly of 4,000 molecular weight. They alsopreferably do not contain block copolymers of ethylene oxide andpropylene oxide, like PLURONIC L101.

Other suds suppressors useful herein comprise the secondary alcohols(e.g., 2-alkyl alkanols) and mixtures of such alcohols with siliconeoils, such as the silicones disclosed in U.S. Pat. No. 4,798,679, U.S.Pat. No. 4,075,118 and EP 150,872. The secondary alcohols include the C₆-C₁₆ alkyl alcohols having a C₁ -C₁₆ chain. A preferred alcohol is2-butyl octanol, which is available from Condea under the trademarkISOFOL 12. Mixtures of secondary alcohols are available under thetrademark ISALCHEM 123 from Enichem. Mixed suds suppressors typicallycomprise mixtures of alcohol+silicone at a weight ratio of 1:5 to 5:1.

For any detergent compositions to be used in automatic laundry washingmachines, suds should not form to the extent that they overflow thewashing machine. Suds suppressors, when utilized, are preferably presentin a "suds suppressing amount. By "suds suppressing amount" is meantthat the formulator of the composition can select an amount of this sudscontrolling agent that will sufficiently control the suds to result in alow-sudsing laundry detergent for use in automatic laundry washingmachines.

The compositions herein will generally comprise from 0% to about 10% ofsuds suppressor. When utilized as suds suppressors, monocarboxylic fattyacids, and salts therein, will be present typically in amounts up toabout 5%, by weight, of the detergent composition. Preferably, fromabout 0.5% to about 3% of fatty monocarboxylate suds suppressor isutilized. Silicone suds suppressors are typically utilized in amounts upto about 2.0%, by weight, of the detergent composition, although higheramounts may be used. This upper limit is practical in nature, dueprimarily to concern with keeping costs minimized and effectiveness oflower amounts for effectively controlling sudsing. Preferably from about0.01% to about 1% of silicone suds suppressor is used, more preferablyfrom about 0.25% to about 0.5%. As used herein, these weight percentagevalues include any silica that may be utilized in combination withpolyorganosiloxane, as well as any adjunct materials that may beutilized. Monostearyl phosphate suds suppressors are generally utilizedin amounts ranging from about 0.1% to about 2%, by weight, of thecomposition. Hydrocarbon suds suppressors are typically utilized inamounts ranging from about 0.01% to about 5.0%, although higher levelscan be used. The alcohol suds suppressors are typically used at 0.2%-3%by weight of the finished compositions.

Alkoxylated Polycarboxylates--Alkoxylated polycarboxylates such as thoseprepared from polyacrylates are useful herein to provide additionalgrease removal performance. Such materials are described in WO 91/08281and PCT 90/01815 at p. 4 et seq., incorporated herein by reference.Chemically, these materials comprise polyacrylates having one ethoxyside-chain per every 7-8 acrylate units. The side-chains are of theformula --(CH₂ CH₂ O)_(m) (CH₂)_(n) CH₃ wherein m is 2-3 and n is 6-12.The side-chains are ester-linked to the polyacrylate "backbone" toprovide a "comb" polymer type structure. The molecular weight can vary,but is typically in the range of about 2000 to about 50,000. Suchalkoxylated polycarboxylates can comprise from about 0.05% to about 10%,by weight, of the compositions herein.

Fabric Softeners--Various through-the-wash fabric softeners, especiallythe impalpable smectite clays of U.S. Pat. No. 4,062,647, Storm andNirschl, issued Dec. 13, 1977, as well as other softener clays known inthe art, can optionally be used typically at levels of from about 0.5%to about 10% by weight in the present compositions to provide fabricsoftener benefits concurrently with fabric cleaning. Clay softeners canbe used in combination with amine and cationic softeners as disclosed,for example, in U.S. Pat. No. 4,375,416, Crisp et al, March 1, 1983 andU.S. Pat. No. 4,291,071, Harris et al, issued Sep. 22, 1981.

Perfumes--Perfumes and perfumery ingredients useful in the presentcompositions and processes comprise a wide variety of natural andsynthetic chemical ingredients, including, but not limited to,aldehydes, ketones, esters, and the like. Also included are variousnatural extracts and essences which can comprise complex mixtures ofingredients, such as orange oil, lemon oil, rose extract, lavender,musk, patchouli, balsamic essence, sandalwood oil, pine oil, cedar, andthe like. Finished perfumes can comprise extremely complex mixtures ofsuch ingredients. Finished perfumes typically comprise from about 0.01%to about 2%, by weight, of the detergent compositions herein, andindividual perfumery ingredients can comprise from about 0.0001% toabout 90% of a finished perfume composition.

Several perfume formulations are set forth in Example XXI, hereinafter.Non-limiting examples of perfume ingredients useful herein include:7-acetyl-1,2,3,4,5,6,7,8-octahydro-1,1,6,7-tetramethyl naphthalene;ionone methyl; ionone gamma methyl; methyl cedrylone; methyldihydrojasmonate; methyl 1,6,10-trimethyl-2,5,9-cyclododecatrien-1-ylketone; 7-acetyl-1,1,3,4,4,6-hexamethyl tetralin;4-acetyl-6-tert-butyl-1,1-dimethyl indane; para-hydroxy-phenyl-butanone;benzophenone; methyl beta-naphthyl ketone;6-acetyl-1,1,2,3,3,5-hexamethyl indane;5-acetyl-3-isopropyl-1,1,2,6-tetramethyl indane; 1-dodecanal,4-(4-hydroxy-4-methyl-pentyl)-3-cyclohexene-1-carboxaldehyde;7-hydroxy-3,7-dimethyl ocatanal; 10-undecen-1-al; iso-hexenyl cyclohexylcarboxaldehyde; formyl tricyclodecane; condensation products ofhydroxycitronellal and methyl anthranilate, condensation products ofhydroxycitronellal and indol, condensation products of phenylacetaldehyde and indol;2-methyl-3-(para-tert-butylphenyl)-propionaldehyde; ethyl vanillin,heliotropin; hexyl cinnamic aldehyde; amyl cinnamic aldehyde;2-methyl-2-(para-iso-propylphenyl)-propionaldehyde; coumarin;decalactone gamma; cyclo-pentadecanolide; 16-hydroxy-9-hexadecenoic acidlactone; 1,3,4,6,7,8-hexahydro-4,6,6,7,8,8-hexamethylcyclopenta-gamma-2-benzopyrane;beta-naphthol methyl ether; ambroxane;dodecahydro-3a,6,6,9a-tetramethylnaphtho[2,1b]furan; cedrol,5-(2,2,3-trimethylcyclopent-3-enyl)-3-methylpentan-2-ol;2-ethyl-4-(2,2,3-trimethyl-3-cyclopenten-1-yl)-2-buten-1-ol;caryophyllene alcohol; tricyclodecenyl propionate; tricyclodecenylacetate; benzyl salicylate; cedryl acetate; and para-(tert-butyl)cyclohexyl acetate.

Particularly preferred perfume materials are those that provide thelargest odor improvements in finished product compositions containingcellulases. These perfumes include but are not limited to: hexylcinnamic aldehyde; 2-methyl-3-(para-tert-butylphenyl)-propionaldehyde;7-acetyl-1,2,3,4,5,6,7,8-octahydro-1,1,6,7-tetra-methyl naphthalene;benzyl salicylate; 7-acetyl-1,1,3,4,4,6-hexamethyl tetralin;para-tert-butyl cyclohexyl acetate; methyl dihydro jasmonate;beta-napthol methyl ether; methyl beta-naphthyl ketone;2-methyl-2-(para-iso-propylphenyl)-propionaldehyde;1,3,4,6,7,8-hexahydro-4,6,6,7,8,8-hexamethyl-cyclopenta-gamma-2-benzopyrane;dodecahydro-3a,6,6,9a-tetramethylnaphtho[2,1b]furan; anisaldehyde;coumarin; cedrol; vanillin; cyclopentadecanolide; tricyclodecenylacetate; and tricyclodecenyl propionate.

Other perfume materials include essential oils, resinoids, and resinsfrom a variety of sources including, but not limited to: Peru balsam,Olibanum resinoid, styrax, labdanum resin, nutmeg, cassia oil, benzoinresin, coriander and lavandin. Still other perfume chemicals includephenyl ethyl alcohol, terpineol, linalool, linalyl acetate, geraniol,nerol, 2-(1,1-dimethylethyl)-cyclohexanol acetate, benzyl acetate, andeugenol. Carriers such as diethylphthalate can be used in the finishedperfume compositions.

Other Ingredients--A wide variety of other ingredients useful indetergent compositions can be included in the compositions herein,including other active ingredients, carriers, hydrotropes, processingaids, dyes or pigments, solvents for liquid formulations, solid fillersfor bar compositions, etc. If high sudsing is desired, suds boosterssuch as the C₁₀ -C₁₆ alkanolamides can be incorporated into thecompositions, typically at 1%-10% levels. The C₁₀ -C₁₄ monoethanol anddiethanol amides illustrate a typical class of such suds boosters. Useof such suds boosters with high sudsing adjunct surfactants such as theamine oxides, betaines and sultaines noted above is also advantageous.If desired, water-soluble magnesium and/or calcium salts such as MgCl₂,MgSO₄, CaCl₂, CaSO₄ and the like, can be added at levels of, typically,0.1%-2%, to provide additional suds and to enhance grease removalperformance.

Various detersive ingredients employed in the present compositionsoptionally can be further stabilized by absorbing said ingredients ontoa porous hydrophobic substrate, then coating said substrate with ahydrophobic coating. Preferably, the detersive ingredient is admixedwith a surfactant before being absorbed into the porous substrate. Inuse, the detersive ingredient is released from the substrate into theaqueous washing liquor, where it performs its intended detersivefunction.

To illustrate this technique in more detail, a porous hydrophobic silica(trademark SIPERNAT D10, DeGussa) is admixed with a proteolytic enzymesolution containing 3%-5% of C₁₃₋₁₅ ethoxylated alcohol (EO 7) nonionicsurfactant. Typically, the enzyme/surfactant solution is 2.5× the weightof silica. The resulting powder is dispersed with stirring in siliconeoil (various silicone oil viscosities in the range of 500-12,500 can beused). The resulting silicone oil dispersion is emulsified or otherwiseadded to the final detergent matrix. By this means, ingredients such asthe aforementioned enzymes, bleaches, bleach activators, bleachcatalysts, photoactivators, dyes, fluorescers, fabric conditioners andhydrolyzable surfactants can be "protected" for use in detergents,including liquid laundry detergent compositions.

Liquid detergent compositions can contain water and other solvents ascarriers. Low molecular weight primary or secondary alcohols exemplifiedby methanol, ethanol, propanol, and isopropanol are suitable. Monohydricalcohols are preferred for solubilizing surfactant, but polyols such asthose containing from 2 to about 6 carbon atoms and from 2 to about 6hydroxy groups (e.g., 1,3-propanediol, ethylene glycol, glycerine, and1,2-propanediol) can also be used. The compositions may contain from 5%to 90%, typically 10% to 50% of such carriers.

The detergent compositions herein will preferably be formulated suchthat, during use in aqueous cleaning operations, the wash water willhave a pH of between about 6.5 and about 11, preferably between about7.5 and 10.5. Liquid dishwashing product formulations preferably have apH between about 6.8 and about 9.0. Laundry products are typically at pH9-11. Techniques for controlling pH at recommended usage levels includethe use of buffers, alkalis, acids, etc., and are well known to thoseskilled in the art.

Form of the Compositions

The compositions in accordance with the invention can take a variety ofphysical forms including granular, tablet, bar and liquid forms. Thecompositions are particularly the so-called concentrated granulardetergent compositions adapted to be added to a washing machine by meansof a dispensing device placed in the machine drum with the soiled fabricload.

The mean particle size of the components of granular compositions inaccordance with the invention should preferably be such that no morethat 5% of particles are greater than 1.7 mm in diameter and not morethan 5% of particles are less than 0.15 mm in diameter.

The term mean particle size as defined herein is calculated by sieving asample of the composition into a number of fractions (typically 5fractions) on a series of Tyler sieves. The weight fractions therebyobtained are plotted against the aperture size of the sieves. The meanparticle size is taken to be the aperture size through which 50% byweight of the sample would pass.

The bulk density of granular detergent compositions in accordance withthe present invention typically have a bulk density of at least 600g/litre, more preferably from 650 g/litre to 1200 g/litre. Bulk densityis measured by means of a simple funnel and cup device consisting of aconical funnel moulded rigidly on a base and provided with a flap valveat its lower extremity to allow the contents of the funnel to be emptiedinto an axially aligned cylindrical cup disposed below the funnel. Thefunnel is 130 mm high and has internal diameters of 130 mm and 40 mm atits respective upper and lower extremities. It is mounted so that thelower extremity is 140 mm above the upper surface of the base. The cuphas an overall height of 90 mm, an internal height of 87 mm and aninternal diameter of 84 mm. Its nominal volume is 500 ml.

To carry out a measurement, the funnel is filled with powder by handpouring, the flap valve is opened and powder allowed to overfill thecup. The filled cup is removed from the frame and excess powder removedfrom the cup by passing a straight edged implement eg; a knife, acrossits upper edge. The filled cup is then weighed and the value obtainedfor the weight of powder doubled to provide a bulk density in g/litre.Replicate measurements are made as required.

Mid-chain Branched Surfactant Agglomerate Particles

The mid-chain branched surfactant system herein is preferably present ingranular compositions in the form of mid-chain branched surfactantagglomerate particles, which may take the form of flakes, prills,marumes, noodles, ribbons, but preferably take the form of granules. Themost preferred way to process the particles is by agglomerating powders(e.g. aluminosilicate, carbonate) with high active mid-chain branchedsurfactant pastes and to control the particle size of the resultantagglomerates within specified limits. Such a process involves mixing aneffective amount of powder with a high active mid-chain branchedsurfactant paste in one or more agglomerators such as a panagglomerator, a Z-blade mixer or more preferably an in-line mixer suchas those manufactured by Schugi (Holland) BV, 29 Chroomstraat 8211 AS,Lelystad, Netherlands, and Gebruder Lodige Maschinenbau GmbH, D-4790Paderborn 1, Elsenerstrasse 7-9, Postfach 2050, Germany. Most preferablya high shear mixer is used, such as a Lodige CB (Trade Name).

A high active mid-chain branched surfactant paste comprising from 50% byweight to 95% by weight, preferably 70% by weight to 85% by weight ofmid-chain branched surfactant is typically used. The paste may be pumpedinto the agglomerator at a temperature high enough to maintain apumpable viscosity, but low enough to avoid degradation of the anionicsurfactants used. An operating temperature of the paste of 50° C. to 80°C. is typical.

Laundry washing method

Machine laundry methods herein typically comprise treating soiledlaundry with an aqueous wash solution in a washing machine havingdissolved or dispensed therein an effective amount of a machine laundrydetergent composition in accord with the invention. By an effectiveamount of the detergent composition it is meant from 40 g to 300 g ofproduct dissolved or dispersed in a wash solution of volume from 5 to 65litres, as are typical product dosages and wash solution volumescommonly employed in conventional machine laundry methods.

As noted, the mid-chain branched surfactant surfactants are used hereinin detergent compositions, preferably in combination with otherdetersive surfactants, at levels which are effective for achieving atleast a directional improvement in cleaning performance. In the contextof a fabric laundry composition, such "usage levels" can vary dependingnot only on the type and severity of the soils and stains, but also onthe wash water temperature, the volume of wash water and the type ofwashing machine.

For example, in a top-loading, vertical axis U.S.-type automatic washingmachine using about 45 to 83 liters of water in the wash bath, a washcycle of about 10 to about 14 minutes and a wash water temperature ofabout 10° C. to about 50° C., it is preferred to include from about 2ppm to about 625 ppm, preferably from about 2 ppm to about 550 ppm, morepreferably from about 10 ppm to about 235 ppm, of the mid-chain branchedsurfactant surfactant in the wash liquor. On the basis of usage rates offrom about 50 ml to about 150 ml per wash load, this translates into anin-product concentration (wt.) of the mid-chain branched surfactantsurfactant of from about 0.1% to about 40%, preferably about 0.1% toabout 35%, more preferably from about 0.5% to about 15%, for aheavy-duty liquid laundry detergent. On the basis of usage rates of fromabout 30 g to about 950 g per wash load, for dense ("compact") granularlaundry detergents (density above about 650 g/l) this translates into anin-product concentration (wt.) of the mid-chain branched surfactantsurfactant of from about 0.1% to about 50%, preferably from about 0.1%to about 35%, and more preferably from about 0.5% to about 15%. On thebasis of usage rates of from about 80 g to about 100 g per load forspray-dried granules (i.e., "fluffy"; density below about 650 g/l), thistranslates into an in-product concentration (wt.) of the mid-chainbranched surfactant surfactant of from about 0.07% to about 35%,preferably from about 0.07 to about 25%, and more preferably from about0.35% to about 11%.

For example, in a front-loading, horizontal-axis European-type automaticwashing machine using about 8 to 15 liters of water in the wash bath, awash cycle of about 10 to about 60 minutes and a wash water temperatureof about 30° C. to about 95° C., it is preferred to include from about 3ppm to about 14,000 ppm, preferably from about 3 ppm to about 10,000ppm, more preferably from about 15 ppm to about 4200 ppm, of themid-chain branched surfactant surfactant in the wash liquor. On thebasis of usage rates of from about 45 ml to about 270 ml per wash load,this translates into an in-product concentration (wt.) of the mid-chainbranched surfactant surfactant of from about 0.1% to about 50%,preferably about 0.1% to about 35%, more preferably from about 0.5% toabout 15%, for a heavy-duty liquid laundry detergent. On the basis ofusage rates of from about 40 g to about 210 g per wash load, for dense("compact") granular laundry detergents (density above about 650 g/l)this translates into an in-product concentration (wt.) of the mid-chainbranched surfactant surfactant of from about 0.12% to about 53%,preferably from about 0.12% to about 46%, and more preferably from about0.6% to about 20%. On the basis of usage rates of from about 140 g toabout 400 g per load for spray-dried granules (i.e., "fluffy"; densitybelow about 650 g/l), this translates into an in-product concentration(wt.) of the mid-chain branched surfactant surfactant of from about0.03% to about 34%, preferably from about 0.03% to about 24%, and morepreferably from about 0.15% to about 10%.

For example, in a top-loading, vertical-axis Japanese-type automaticwashing machine using about 26 to 52 liters of water in the wash bath, awash cycle of about 8 to about 15 minutes and a wash water temperatureof about 5° C. to about 25° C., it is preferred to include from about0.67 ppm to about 270 ppm, preferably from about 0.67 ppm to about 236ppm, more preferably from about 3.4 ppm to about 100 ppm, of themid-chain branched surfactant surfactant in the wash liquor. On thebasis of usage rates of from about 20 ml to about 30 ml per wash load,this translates into an in-product concentration (wt.) of the mid-chainbranched surfactant surfactant of from about 0.1% to about 40%,preferably about 0.1% to about 35%, more preferably from about 0.5% toabout 15%, for a heavy-duty liquid laundry detergent. On the basis ofusage rates of from about 18 g to about 35 g per wash load, for dense("compact") granular laundry detergents (density above about 650 g/l)this translates into an in-product concentration (wt.) of the mid-chainbranched surfactant surfactant of from about 0.1% to about 50%,preferably from about 0.1% to about 35%, and more preferably from about0.5% to about 15%. On the basis of usage rates of from about 30 g toabout 40 g per load for spray-dried granules (i.e., "fluffy"; densitybelow about 650 g/l), this translates into an in-product concentration(wt.) of the mid-chain branched surfactant surfactant of from about0.06% to about 44%, preferably from about 0.06% to about 30%, and morepreferably from about 0.3% to about 13%.

As can be seen from the foregoing, the amount of mid-chain branchedsurfactant surfactant used in a machine-wash laundering context canvary, depending on the habits and practices of the user, the type ofwashing machine, and the like. In this context, however, one heretoforeunappreciated advantage of the mid-chain branched surfactant surfactantsis their ability to provide at least directional improvements inperformance over a spectrum of soils and stains even when used atrelatively low levels with respect to the other surfactants (generallyanionics or anionic/nonionic mixtures) in the finished compositions.

In a preferred use aspect a dispensing device is employed in the washingmethod. The dispensing device is charged with the detergent product, andis used to introduce the product directly into the drum of the washingmachine before the commencement of the wash cycle. Its volume capacityshould be such as to be able to contain sufficient detergent product aswould normally be used in the washing method.

Once the washing machine has been loaded with laundry the dispensingdevice containing the detergent product is placed inside the drum. Atthe commencement of the wash cycle of the washing machine water isintroduced into the drum and the drum periodically rotates. The designof the dispensing device should be such that it permits containment ofthe dry detergent product but then allows release of this product duringthe wash cycle in response to its agitation as the drum rotates and alsoas a result of its contact with the wash water.

To allow for release of the detergent product during the wash the devicemay possess a number of openings through which the product may pass.Alternatively, the device may be made of a material which is permeableto liquid but impermeable to the solid product, which will allow releaseof dissolved product. Preferably, the detergent product will be rapidlyreleased at the start of the wash cycle thereby providing transientlocalised high concentrations of product in the drum of the washingmachine at this stage of the wash cycle.

Preferred dispensing devices are reusable and are designed in such a waythat container integrity is maintained in both the dry state and duringthe wash cycle. Especially preferred dispensing devices for use with thecomposition of the invention have been described in the followingpatents; GB-B-2, 157, 717, GB-B-2, 157, 718, EP-A-0201376, EP-A-0288345and EP-A-0288346. An article by J. Bland published in ManufacturingChemist, November 1989, pages 41-46 also describes especially preferreddispensing devices for use with granular laundry products which are of atype commonly know as the "granulette". Another preferred dispensingdevice for use with the compositions of this invention is disclosed inPCT Patent Application No. W094/11562.

Especially preferred dispensing devices are disclosed in European PatentApplication Publication Nos. 0343069 & 0343070. The latter Applicationdiscloses a device comprising a flexible sheath in the form of a bagextending from a support ring defining an orifice, the orifice beingadapted to admit to the bag sufficient product for one washing cycle ina washing process. A portion of the washing medium flows through theorifice into the bag, dissolves the product, and the solution thenpasses outwardly through the orifice into the washing medium. Thesupport ring is provided with a masking arrangement to prevent egress ofwetted, undissolved, product, this arrangement typically comprisingradially extending walls extending from a central boss in a spoked wheelconfiguration, or a similar structure in which the walls have a helicalform.

Alternatively, the dispensing device may be a flexible container, suchas a bag or pouch. The bag may be of fibrous construction coated with awater impermeable protective material so as to retain the contents, suchas is disclosed in European published Patent Application No. 0018678.Alternatively it may be formed of a water-insoluble synthetic polymericmaterial provided with an edge seal or closure designed to rupture inaqueous media as disclosed in European published Patent Application Nos.0011500, 0011501, 0011502, and 0011968. A convenient form of waterfrangible closure comprises a water soluble adhesive disposed along andsealing one edge of a pouch formed of a water impermeable polymeric filmsuch as polyethylene or polypropylene.

Machine Dishwashing Method

Any suitable methods for machine washing or cleaning soiled tableware,particularly soiled silverware are envisaged.

A preferred machine dishwashing method comprises treating soiledarticles selected from crockery, glassware, hollowware, silverware andcutlery and mixtures thereof with an aqueous liquid having dissolved ordispensed therein an effective amount of a machine dishwashingcomposition in accord with the invention. By an effective amount of themachine dishwashing composition it is meant from 8 g to 60 g of productdissolved or dispersed in a wash solution of volume from 3 to 10 litres,as are typical product dosages and wash solution volumes commonlyemployed in conventional machine dishwashing methods.

Packaging for the Compositions

Commercially marketed executions of the bleaching compositions can bepackaged in any suitable container including those constructed frompaper, cardboard, plastic materials and any suitable laminates. Apreferred packaging execution is described in European Application No.94921505.7.

In the following Examples, the abbreviations for the various ingredientsused for the compositions have the following meanings.

    ______________________________________                                        LAS       Sodium linear C.sub.12  alkyl benzene sulfonate                       MBAS.sub.x Mid-chain branched primary alkyl (average total                     carbons = x) sulfate                                                         MBAE.sub.x S.sub.z Mid-chain branched primary alkyl (average total                      carbons = z) ethoxylate (average EO = x) sulfate,                    sodium salt                                                                  MBAE.sub.x Mid-chain branched primary alkyl (average total                     carbons = x) ethoxylate (average EO = 8)                                     C45AS Sodium C.sub.14 -C.sub.15  linear alkyl sulfate                         CxyEzS Sodium C.sub.1x -C.sub.1y  branched alkyl sulfate                       condensed with z moles of ethylene oxide                                     CxyEz A C.sub.1x-1y  branched primary alcohol condensed                        with an average of z moles of ethylene oxide                                 QAS R.sub.2.N.sup.+ (CH.sub.3).sub.2 (C.sub.2 H.sub.4 OH) with R.sub.2                = C.sub.12 -C.sub.14                                                  TFAA C.sub.16 -C.sub.18  alkyl N-methyl glucamide                             STPP Anhydrous sodium tripolyphosphate                                        Zeolite A Hydrated Sodium Aluminosilicate of formula                           Na.sub.12 (A10.sub.2 SiO.sub.2).sub.12.27H.sub.2 O having a primary                    particle size in the range from 0.1 to 10                            micrometers                                                                  NaSKS-6 Crystalline layered silicate of formula                                δ-Na.sub.2 Si.sub.2 O.sub.5                                            Carbonate Anhydrous sodium carbonate with a particle size                      between 200 μm and 900 μm                                              Bicarbonate Anhydrous sodium bicarbonate with a particle size                  distribution between 400 μm and 1200 μm                                Silicate Amorphous Sodium Silicate (SiO.sub.2 :Na.sub.2 O; 2.0                 ratio)                                                                       Sodium sulfate Anhydrous sodium sulfate                                       MA/AA Copolymer of 1:4 maleic/acrylic acid, average                            molecular weight about 70,000                                                CMC Sodium carboxymethyl cellulose                                            Protease Proteolytic enzyme of activity 4 KNPU/g sold by                       NOVO Industries A/S under the tradename                                       Savinase                                                                     Cellulase Cellulytic enzyme of activity 1000 CEVU/g sold                       by NOVO Industries A/S under the tradename                                    Carezyme                                                                     Amylase Amylolytic enzyme of activity 60 KNU/g sold by                         NOVO Industries A/S under the tradename                                       Termamyl 60T                                                                 Lipase Lipolytic enzyme of activity 100 kLU/g sold by                          NOVO Industries A/S under the tradename                                       Lipolase                                                                     PB4 Sodium perborate tetrahydrate of nominal formula                           NaBO.sub.2.3H.sub.2 O.H.sub.2 O.sub.2                                        PB1 Anhydrous sodium perborate bleach of                                       nominal formula NaBO.sub.2.H.sub.2 O.sub.2                                   Percarbonate Sodium Percarbonate of nominal formula                            2Na.sub.2 CO.sub.3.3H.sub.2 O.sub.2                                          NaDCC Sodium dichloroisocyanurate                                             NOBS Nonanoyloxybenzene sulfonate in the form of the                           sodium salt                                                                  TAED Tetraacetylethylenediamine                                               DTPMP Diethylene triamine penta (methylene phosphonate),                       marketed by Monsanto under the Trade name Dequest                             2060                                                                         Photoactivated Sulfonated Zinc Phthlocyanine encapsulated in                  bleach dextrin soluble polymer                                                Brightener 1 Disodium 4,4'-bis(2-sulphostyryl)biphenyl                        Brightener 2 Disodium 4,4'-bis(4-anilino-6-morpholino-1.3.5-                   triazin-2-yl)amino) stilbene-2:2'-disulfonate                                HEDP 1,1-hydroxyethane diphosphonic acid                                      SRP 1 Sulfobenzoyl end capped esters with oxyethylene                          oxy and terephtaloyl backbone                                                Silicone antifoam Polydimethylsiloxane foam controller with siloxane-                   oxyalkylene copolymer as dispersing agent with a ratio                        of said foam controller to said dispersing agent of 10:1                      to 100:1                                                            DTPA Diethylene triamine pentaacetic acid                                   ______________________________________                                    

In the following Examples all levels are quoted as % by weight of thecomposition. The following examples are illustrative of the presentinvention, but are not meant to limit or otherwise define its scope. Allparts, percentages and ratios used herein are expressed as percentweight unless otherwise specified.

EXAMPLE 1

The following laundry detergent compositions A to F are prepared inaccord with the invention:

    ______________________________________                                               A     B       C       D     E     F                                    ______________________________________                                        MBAS.sub.16.5                                                                          8.0     8.0     8.0   8.0   8.0   8.0                                  C25E3 3.4 3.4 3.4 3.4 3.4 3.4                                                 QAS --  0.8 --  --  0.8 --                                                    QAS -- --  0.8 -- --  0.8                                                     Zeolite A 18.1 18.1 18.1 18.1 18.1 18.1                                       Carbonate 13.0 13.0 13.0 27.0 27.0 27.0                                       Silicate 1.4 1.4 1.4 3.0 3.0 3.0                                              Sodium sulfate 26.1 26.1 26.1 26.1 26.1 26.1                                  PB4 9.0 9.0 9.0 9.0 9.0 9.0                                                   TAED 1.5 1.5 1.5 1.5 1.5 1.5                                                  DETPMP 0.25 0.25 0.25 0.25 0.25 0.25                                          HEDP 0.3 0.3 0.3 0.3 0.3 0.3                                                  Protease 0.26 0.26 0.26 0.26 0.26 0.26                                        Amylase 0.1 0.1 0.1 0.1 0.1 0.1                                               MA/AA 0.3 0.3 0.3 0.3 0.3 0.3                                                 CMC 0.2 0.2 0.2 0.2 0.2 0.2                                                   Photoactivated 15 ppm 15 ppm 15 ppm 15 ppm 15 ppm 15 ppm                      bleach (ppm)                                                                  Brightener 1 0.09 0.09 0.09 0.09 0.09 0.09                                    Perfume 0.3 0.3 0.3 0.3 0.3 0.3                                               Silicone 0.5 0.5 0.5 0.5 0.5 0.5                                              antifoam                                                                      Misc/minors                                                                   to 100%                                                                       Density 850 850 850 850 850 850                                               in g/liter                                                                  ______________________________________                                    

EXAMPLE 2

The following granular laundry detergent compositions G to I of bulkdensity 750 g/litre are prepared in accord with the invention:

    ______________________________________                                                       G       H       I                                              ______________________________________                                        MBAE.sub.2 S.sub.16.5                                                                          5.25      5.61    4.76                                         C45AS --  2.24 3.89                                                           C25AE3S -- 0.76 1.18                                                          C45E7 3.25 --  5.0                                                            C25E3 --  5.5 --                                                              QAS 0.8 2.0 2.0                                                               STPP 10.7 --  --                                                              Zeolite A 10.7 19.5 19.5                                                      SKS-6 --  10.6 10.6                                                           Carbonate 6.1 21.4 21.4                                                       Bicarbonate --  2.0 2.0                                                       Silicate 6.8 --  --                                                           Sodium sulfate 39.8 -- 14.3                                                   PB4 5.0 12.7 8.0                                                              TAED 0.5 3.1 --                                                               DETPMP 0.25 0.2 0.2                                                           HEDP --  0.3 0.3                                                              Protease 0.26 0.85 0.85                                                       Lipase 0.15 0.15 0.15                                                         Cellulase 0.28 0.28 0.28                                                      Amylase 0.1 0.1 0.1                                                           MA/AA 0.8 1.6 1.6                                                             CMC 0.2 0.4 0.4                                                               Photoactivated bleach (ppm) 15 ppm 27 ppm 27 ppm                              Brightener 1 0.08 0.19 0.19                                                   Brightener 2 -- 0.04 0.04                                                     Perfume 0.3 0.3 0.3                                                           Silicone antifoam 0.5 2.4 2.4                                                 Minors/misc to 100%                                                         ______________________________________                                    

EXAMPLE 3

The following detergent formulations, according to the present inventionare prepared:

    ______________________________________                                                    J     K         L      M                                          ______________________________________                                        LAS           15.0    14.0      14.0 18.0                                       MBAE.sub.16 2.7 1.0 3.0 6.0                                                   TFAA --  1.0 --  --                                                           C25E5/C45E7 -- 2.0 -- 0.5                                                     C45E3S -- 2.5 -- --                                                           Zeolite A 30.0 18.0 30.0 22.0                                                 Silicate 9.0 5.0 10.0 8.0                                                     Carbonate 13.0 7.5 --  5.0                                                    Bicarbonate --  7.5 -- --                                                     DTPMP 0.7 1.0 -- --                                                           SRP 1 0.3 0.2 -- 0.1                                                          MA/AA 2.0 1.5 2.0 1.0                                                         CMC 0.8 0.4 0.4 0.2                                                           Protease 0.8 1.0 0.5 0.5                                                      Amylase 0.8 0.4 --  0.25                                                      Lipase 0.2 0.1 0.2 0.1                                                        Cellulase 0.15 0.05 --  --                                                    Photoactivated 70 ppm 45 ppm -- 10 ppm                                        bleach (ppm)                                                                  Brightener 1 0.2 0.2 0.08 0.2                                                 PB1 6.0 2.0 5.0 3.0                                                           NOBS 2.0 1.0 --  --                                                           Polyethylene oxide --  0.2 -- 0.2                                             of MW 5,000,000                                                               Bentonite clay -- --  -- 10.0                                                 Balance (Moisture 100 100 100 100                                             and Miscellaneous)                                                          ______________________________________                                    

EXAMPLE 4

The following high density detergent formulations, according to thepresent invention are prepared:

    ______________________________________                                                             N    O                                                   ______________________________________                                        Agglomerate                                                                     C45AS 11.0 14.0                                                               MBAE.sub.2 S.sub.15 3.0 3.0                                                   Zeolite A 15.0 10.0                                                           Carbonate 4.0 8.0                                                             MA/AA 4.0 2.0                                                                 CMC 0.5 0.5                                                                   DTPMP 0.4 0.4                                                                 Spray On                                                                      C25E5 5.0 5.0                                                                 Perfume 0.5 0.5                                                               Dry Adds                                                                      C.sub.20  SADS 6.0 3.0                                                        HEDP 0.5 0.3                                                                  SKS-6 13.0 6.0                                                                Citrate 3.0 1.0                                                               TAED 5.0 7.0                                                                  Percarbonate 20.0 20.0                                                        SRP 1 0.3 0.3                                                                 Protease 1.4 1.4                                                              Lipase 0.4 0.4                                                                Cellulase 0.6 0.6                                                             Amylase 0.6 0.6                                                               Silicone antifoam 5.0 5.0                                                     Brightener 1 0.2 0.2                                                          Brightener 2 0.2 --                                                           Balance (Moisture and Miscellaneous) 100 100                                  Density (g/liter) 850 850                                                   ______________________________________                                    

The manufacture of heavy duty liquid detergent compositions, especiallythose designed for fabric laundering, which comprise a non-aqueouscarrier medium can be conducted in the manner disclosed in more detailhereinafter. In an alternate mode, such non-aqueous compositions can beprepared according to the disclosures of U.S. Pat. Nos. 4,753,570;4,767,558; 4,772,413; 4,889,652; 4,892,673; GB-A-2,158,838;GB-A-2,195,125; GB-A-2,195,649; U.S. Pat. No. 4,988,462; U.S. Pat. No.5,266,233; EP-A-225,654 (Jun. 16, 1987); EP-A-510,762 (Oct. 28, 1992);EP-A-540,089 (May 5, 1993); EP-A-540,090 (May 5, 1993); U.S. Pat. No.4,615,820; EP-A-565,017 (Oct 13, 1993); EP-A-030,096 (Jun 10, 1981),incorporated herein by reference. Such compositions can contain variousparticulate detersive ingredients (including the bleaching agents, asdisclosed hereinabove) stably suspended therein. Such non-aqueouscompositions thus comprise a LIQUID PHASE and, optionally butpreferably, a SOLID PHASE, all as described in more detail hereinafterand in the cited references. The mid-chain branched surfactant isincorporated in the compositions at the levels and in the mannerdescribed hereinabove for the manufacture of other laundry detergentcompositions.

Liquid Phase

The liquid phase will generally comprise from about 35% to 99% by weightof the detergent compositions herein. More preferably, the liquid phasewill comprise from about 50% to 95% by weight of the compositions. Mostpreferably, the liquid phase will comprise from about 45% to 75% byweight of the compositions herein. The liquid phase of the detergentcompositions herein essentially contains relatively high concentrationsof a certain type anionic surfactant combined with a certain type ofnonaqueous, liquid diluent.

(A) Essential Anionic Surfactant

The anionic surfactant essentially utilized as an essential component ofthe nonaqueous liquid phase is one selected from the alkali metal saltsof alkylbenzene sulfonic acids in which the alkyl group contains fromabout 10 to 16 carbon atoms, in straight chain or branched chainconfiguration. (See U.S. Pat. Nos. 2,220,099 and 2,477,383, incorporatedherein by reference.) Especially preferred are the sodium and potassiumlinear straight chain alkylbenzene sulfonates (LAS) in which the averagenumber of carbon atoms in the alkyl group is from about 11 to 14. SodiumC₁₁ -C₁₄ LAS is especially preferred.

The alkylbenzene sulfonate anionic surfactant will be dissolved in thenonaqueous liquid diluent which makes up the second essential componentof the nonaqueous phase. To form the structured liquid phase requiredfor suitable phase stability and acceptable rheology, the alkylbenzenesulfonate anionic surfactant is generally present to the extent of fromabout 30% to 65% by weight of the liquid phase. More preferably, thealkylbenzene sulfonate anionic surfactant will comprise from about 35%to 50% by weight of the nonaqueous liquid phase of the compositionsherein. Utilization of this anionic surfactant in these concentrationscorresponds to an anionic surfactant concentration in the totalcomposition of from about 15% to 60% by weight, more preferably fromabout 20% to 40% by weight, of the composition.

(B) Nonaqueous Liquid Diluent

To form the liquid phase of the detergent compositions, the hereinbeforedescribed alkylbenzene sulfonate anionic surfactant is combined with anonaqueous liquid diluent which contains two essential components. Thesetwo components are a liquid alcohol alkoxylate material and anonaqueous, low-polarity organic solvent.

i) Alcohol Alkoxylates

One essential component of the liquid diluent used to form thecompositions herein comprises an alkoxylated fatty alcohol material.Such materials are themselves also nonionic surfactants. Such materialscorrespond to the general formula:

    R.sup.1 (C.sub.m H.sub.2m O).sub.n OH

wherein R¹ is a C₈ -C₁₆ alkyl group, m is from 2 to 4, and n ranges fromabout 2 to 12. Preferably R¹ is an alkyl group, which may be primary orsecondary, that contains from about 9 to 15 carbon atoms, morepreferably from about 10 to 14 carbon atoms. Preferably also thealkoxylated fatty alcohols will be ethoxylated materials that containfrom about 2 to 12 ethylene oxide moieties per molecule, more preferablyfrom about 3 to 10 ethylene oxide moieties per molecule.

The alkoxylated fatty alcohol component of the liquid diluent willfrequently have a hydrophilic-lipophilic balance (HLB) which ranges fromabout 3 to 17. More preferably, the HLB of this material will range fromabout 6 to 15, most preferably from about 8 to 15.

Examples of fatty alcohol alkoxylates useful as one of the essentialcomponents of the nonaqueous liquid diluent in the compositions hereinwill include those which are made from alcohols of 12 to 15 carbon atomsand which contain about 7 moles of ethylene oxide. Such materials havebeen commercially marketed under the trade names Neodol 25-7 and Neodol23-6.5 by Shell Chemical Company. Other useful Neodols include Neodol1-5, an ethoxylated fatty alcohol averaging 11 carbon atoms in its alkylchain with about 5 moles of ethylene oxide; Neodol 23-9, an ethoxylatedprimary C₁₂ -C₁₃ alcohol having about 9 moles of ethylene oxide andNeodol 91-10, an ethoxylated C₉ -C₁₁ primary alcohol having about 10moles of ethylene oxide. Alcohol ethoxylates of this type have also beenmarketed by Shell Chemical Company under the Dobanol tradename. Dobanol91-5 is an ethoxylated C₉ -C₁₁ fatty alcohol with an average of 5 molesethylene oxide and Dobanol 25-7 is an ethoxylated C₁₂ -C₁₅ fatty alcoholwith an average of 7 moles of ethylene oxide per mole of fatty alcohol.

Other examples of suitable ethoxylated alcohols include Tergitol 15-S-7and Tergitol 15-S-9 both of which are linear secondary alcoholethoxylates that have been commercially marketed by Union CarbideCorporation. The former is a mixed ethoxylation product of C₁₁ to C₁₅linear secondary alkanol with 7 moles of ethylene oxide and the latteris a similar product but with 9 moles of ethylene oxide being reacted.

Other types of alcohol ethoxylates useful in the present compositionsare higher molecular weight nonionics, such as Neodol 45-11, which aresimilar ethylene oxide condensation products of higher fatty alcohols,with the higher fatty alcohol being of 14-15 carbon atoms and the numberof ethylene oxide groups per mole being about 11. Such products havealso been commercially marketed by Shell Chemical Company.

The alcohol alkoxylate component which is essentially utilized as partof the liquid diluent in the nonaqueous compositions herein willgenerally be present to the extent of from about 1% to 60% of the liquidphase composition. More preferably, the alcohol alkoxylate componentwill comprise about 5% to 40% of the liquid phase. Most preferably, theessentially utilized alcohol alkoxylate component will comprise fromabout 5% to 30% of the detergent composition liquid phase. Utilizationof alcohol alkoxylate in these concentrations in the liquid phasecorresponds to an alcohol alkoxylate concentration in the totalcomposition of from about 1% to 60% by weight, more preferably fromabout 2% to 40% by weight, and most preferably from about 5% to 25% byweight, of the composition.

ii) Nonaqueous Low-Polarity Organic Solvent

A second essential component of the liquid diluent which forms part ofthe liquid phase of the detergent compositions herein comprisesnonaqueous, low-polarity organic solvent(s). The term "solvent" is usedherein to connote the non-surface active carrier or diluent portion ofthe liquid phase of the composition. While some of the essential and/oroptional components of the compositions herein may actually dissolve inthe "solvent"-containing liquid phase, other components will be presentas particulate material dispersed within the "solvent"-containing liquidphase. Thus the term "solvent" is not meant to require that the solventmaterial be capable of actually dissolving all of the detergentcomposition components added thereto.

The nonaqueous organic materials which are employed as solvents hereinare those which are liquids of low polarity. For purposes of thisinvention, "low-polarity" liquids are those which have little, if any,tendency to dissolve one of the preferred types of particulate materialused in the compositions herein, i.e., the peroxygen bleaching agents,sodium perborate or sodium percarbonate. Thus relatively polar solventssuch as ethanol should not be utilized. Suitable types of low-polaritysolvents useful in the nonaqueous liquid detergent compositions hereindo include non-vicinal C₄ -C₈ alkylene glycols, alkylene glycol monolower alkyl ethers, lower molecular weight polyethylene glycols, lowermolecular weight methyl esters and amides, and the like.

A preferred type of nonaqueous, low-polarity solvent for use in thecompositions herein comprises the non-vicinal C₄ -C₈ branched orstraight chain alkylene glycols. Materials of this type include hexyleneglycol (4-methyl-2,4-pentanediol), 1,6-hexanediol, 1,3-butylene glycoland 1,4-butylene glycol. Hexylene glycol is the most preferred.

Another preferred type of nonaqueous, low-polarity solvent for useherein comprises the mono-, di-, tri-, or tetra- C₂ -C₃ alkylene glycolmono C₂ -C₆ alkyl ethers. The specific examples of such compoundsinclude diethylene glycol monobutyl ether, tetraethylene glycolmonobutyl ether, dipropylene glycol monoethyl ether, and dipropyleneglycol monobutyl ether. Diethylene glycol monobutyl ether anddipropylene glycol monobutyl ether are especially preferred. Compoundsof the type have been commercially marketed under the tradenamesDowanol, Carbitol, and Cellosolve.

Another preferred type of nonaqueous, low-polarity organic solventuseful herein comprises the lower molecular weight polyethylene glycols(PEGs). Such materials are those having molecular weights of at leastabout 150. PEGs of molecular weight ranging from about 200 to 600 aremost preferred.

Yet another preferred type of non-polar, nonaqueous solvent compriseslower molecular weight methyl esters. Such materials are those of thegeneral formula: R¹ --C(O)--OCH₃ wherein R¹ ranges from 1 to about 18.Examples of suitable lower molecular weight methyl esters include methylacetate, methyl propionate, methyl octanoate, and methyl dodecanoate.

The nonaqueous, low-polarity organic solvent(s) employed should, ofcourse, be compatible and non-reactive with other compositioncomponents, e.g., bleach and/or activators, used in the liquid detergentcompositions herein. Such a solvent component will generally be utilizedin an amount of from about 1% to 70% by weight of the liquid phase. Morepreferably, the nonaqueous, low-polarity organic solvent will comprisefrom about 10% to 60% by weight of the liquid phase, most preferablyfrom about 20% to 50% by weight, of the liquid phase of the composition.Utilization of this organic solvent in these concentrations in theliquid phase corresponds to a solvent concentration in the totalcomposition of from about 1% to 50% by weight, more preferably fromabout 5% to 40% by weight, and most preferably from about 10% to 30% byweight, of the composition.

iii) Alcohol Alkoxylate To Solvent Ratio

The ratio of alcohol alkoxylate to organic solvent within the liquiddiluent can be used to vary the rheological properties of the detergentcompositions eventually formed. Generally, the weight ratio of alcoholalkoxylate to organic solvent will range from about 50:1 to 1:50. Morepreferably, this ratio will range from about 3:1 to 1:3.

iv) Liquid Diluent Concentration

As with the concentration of the alkylbenzene sulfonate anionicsurfactant mixture, the amount of total liquid diluent in the nonaqueousliquid phase herein will be determined by the type and amounts of othercomposition components and by the desired composition properties.Generally, the liquid diluent will comprise from about 3 5% to 70% ofthe nonaqueous liquid phase of the compositions herein. More preferably,the liquid diluent will comprise from about 50% to 65% of the nonaqueousliquid phase. This corresponds to a nonaqueous liquid diluentconcentration in the total composition of from about 15% to 70% byweight, more preferably from about 20% to 50% by weight, of thecomposition.

Solid Phase

The nonaqueous detergent compositions herein also essentially comprisefrom about 1% to 65% by weight, more preferably from about 5% to 50% byweight, of a solid phase of particulate material which is dispersed andsuspended within the liquid phase. Generally such particulate materialwill range in size from about 0.1 to 1500 microns. More preferably suchmaterial will range in size from about 5 to 200 microns.

The particulate material utilized herein can comprise one or more typesof detergent composition components which in particulate form aresubstantially insoluble in the nonaqueous liquid phase of thecomposition. The types of particulate materials which can be utilizedare described in detail as follows:

Composition Preparation and Use

The nonaqueous liquid detergent compositions herein be prepared bycombining the essential and optional components thereof in anyconvenient order and by mixing, e.g., agitating, the resulting componentcombination to form the phase stable compositions herein. In a typicalprocess for preparing such compositions, essential and certain preferredoptional components will be combined in a particular order and undercertain conditions.

In the first step of such a typical preparation process, an admixture ofthe alkylbenzene sulfonate anionic surfactant and the two essentialcomponents of the nonaqueous diluent is formed by heating a combinationof these materials to a temperature from about 30° C. to 100° C.

In a second process step, the heated admixture formed as hereinbeforedescribed is maintained under shear agitation at a temperature fromabout 40° C. to 100° C. for a period of from about 2 minutes to 20hours. Optionally, a vacuum can be applied to the admixture at thispoint. This second process step serves to completely dissolve theanionic surfactant in the nonaqueous liquid phase.

In a third process step, this liquid phase combination of materials iscooled to a temperature of from about 0° C. to 35° C. This cooling stepserves to form a structured, surfactant-containing liquid base intowhich the particulate material of the detergent compositions herein canbe added and dispersed.

Particulate material is added in a fourth process step by combining theparticulate material with the liquid base which is maintained underconditions of shear agitation. When more than one type of particulatematerial is to be added, it is preferred that a certain order ofaddition be observed. For example, while shear agitation is maintained,essentially all of any optional surfactants in solid particulate formcan be added in the form of particles ranging in size from about 0.2 to1,000 microns. After addition of any optional surfactant particles,particles of substantially all of an organic builder, e.g., citrateand/or fatty acid, and/or an alkalinity source, e.g., sodium carbonate,can be added while continuing to maintain this admixture of compositioncomponents under shear agitation. Other solid form optional ingredientscan then be added to the composition at this point. Agitation of themixture is continued, and if necessary, can be increased at this pointto form a uniform dispersion of insoluble solid phase particulateswithin the liquid phase.

After some or all of the foregoing solid materials have been added tothis agitated mixture, the particles of the bleaching agent can be addedto the composition, again while the mixture is maintained under shearagitation. By adding the bleaching agent material last, or after all ormost of the other components, and especially after alkalinity sourceparticles, have been added, desirable stability benefits for the bleachcan be realized. If enzyme prills are incorporated, they are preferablyadded to the nonaqueous liquid matrix last.

As a final process step, after addition of all of the particulatematerial, agitation of the mixture is continued for a period of timesufficient to form compositions having the requisite viscosity and phasestability characteristics. Frequently this will involve agitation for aperiod of from about 1 to 30 minutes.

As a variation of the composition preparation procedure hereinbeforedescribed, one or more of the solid components may be added to theagitated mixture as a slurry of particles premixed with a minor portionof one or more of the liquid components. Thus a premix of a smallfraction of the alcohol alkoxylate and/or nonaqueous, low-polaritysolvent with particles of the organic builder material and/or theparticles of the inorganic alkalinity source and/or particles of ableach activator may be separately formed and added as a slurry to theagitated mixture of composition components. Addition of such slurrypremixes should precede addition of bleaching agent and/or enzymeparticles which may themselves be part of a premix slurry formed inanalogous fashion.

The compositions of this invention, prepared as hereinbefore described,can be used to form aqueous washing solutions for use in the launderingand bleaching of fabrics. Generally, an effective amount of suchcompositions is added to water, preferably in a conventional fabriclaundering automatic washing machine, to form such aqueouslaundering/bleaching solutions. The aqueous washing/bleaching solutionso formed is then contacted, preferably under agitation, with thefabrics to be laundered and bleached therewith.

An effective amount of the liquid detergent compositions herein added towater to form aqueous laundering/bleaching solutions can compriseamounts sufficient to form from about 500 to 7,000 ppm of composition inaqueous solution. More preferably, from about 800 to 3,000 ppm of thedetergent compositions herein will be provided in aqueouswashing/bleaching solution.

EXAMPLE 5

A non-limiting example of bleach-containing nonaqueous liquid laundrydetergent is prepared having the composition as set forth in Table I.

                  TABLE I                                                         ______________________________________                                        Component             Wt. %   Range (% wt.)                                   ______________________________________                                        Liquid Phase                                                                    Na C.sub.12  Linear alkylbenzene sulfonate (LAS) 25.3 18-35                   MBAS.sub.16.5 2.0 1-3                                                         C.sub.12-14, EO5 alcohol ethoxylate 13.6 10-20                                Hexylene glycol 27.3 20-30                                                    Perfume 0.4   0-1.0                                                           Solids                                                                        Protease enzyme 0.4   0-1.0                                                   Na.sub.3  Citrate, anhydrous 4.3 3-6                                          Sodium perborate 3.4 2-7                                                      Sodium nonanoyloxybenzene sulfonate 8.0  2-12                                 (NOBS)                                                                        Sodium carbonate 13.9  5-20                                                   Diethyl triamine pentaacetic acid (DTPA) 0.9   0-1.5                          Brightener 0.4   0-0.6                                                        Suds Suppressor 0.1   0-0.3                                                   Minors Balance --                                                           ______________________________________                                    

The resulting composition is a stable anhydrous heavy duty liquidlaundry detergent which provides excellent stain and soil removalperformance when used in normal fabric laundering operations.

What is claimed is:
 1. A bleaching detergent composition comprising:a)from about 0.1% to about 50% by weight of a bleaching agent; b) fromabout 0.1% to about 50% by weight of at least one mid-chain branchedsurfactant selected from the group consisting of surfactants having theformula: ##STR46## wherein: (i) one or more C₁ -C₃ alkyl moieties branchfrom the longest linear carbon chain at the positions encompassed by theindicated branching range, with the proviso that said surfactants aresubstantially free of geminal branching; and and wherein further forthis surfactant mixture the average total number of carbon atoms in thebranched primary alkyl moieties having the above formula is within therange of greater than 14.5 to about 17.5;(ii) B is a hydrophilic moietyselected from sulfates, polyoxyalkylene, and alkoxylated sulfates; c)from about 0.1% to about 99.8% by weight of detergent compositionadjunct ingredients; and wherein the composition has an in-use pH in therange of 9-11.
 2. A bleaching detergent composition according to claim 1wherein said bleaching agent is selected from the group consisting ofpercarbonate, perborate, sodium pyrophosphate peroxyhydrate, ureaperoxyhydrate, sodium peroxide, persulfate, percarboxylic acid bleachingagents and salts thereof, and mixtures thereof.
 3. A bleaching detergentcomposition according to claim 2 further comprising a bleach activator.4. A bleaching detergent composition according to claim 2 furthercomprising a bleach catalyst.
 5. A bleaching detergent compositionaccording to claim 1 wherein the bleaching agent comprises a bleachactivator and a persalt selected from the group consisting of perborate,percarbonate, and mixtures thereof.
 6. A bleaching detergent compositionaccording to claim 5 wherein said mid-chain branched surfactant has B assulfate and the branching as methyl, and ##STR47## wherein the totalnumber of carbon atoms in the branched primary alkyl moiety, includingthe [R, R¹, and R² ] branching, is from 14 to
 20. 7. A bleachingdetergent composition according to claim 5 wherein said mid-chainbranched surfactant has B as alkoxy and the branching as methyl, and##STR48## wherein the total number of carbon atoms in the branchedprimary alkyl moiety, including the [R, R¹, and R³ ] branching, but notincluding the carbon atoms in the EO/PO alkoxy moiety, is from 14 to 20.8. A bleaching detergent composition according to claim 5 wherein saidmid-chain branched surfactant has B as alkoxysulfate and the branchingas methyl and ##STR49## wherein the total number of carbon atoms in thebranched primary alkyl moiety, including the [R, R¹, and R² ] branching,but not including the carbon atoms in the EO/PO alkoxy moiety, is from14 to
 20. 9. A granular detergent composition comprising:a) from about1% to about 80% by weight of a builder selected from the groupconsisting of aluminosilicates, silicates, and mixtures thereof, b) fromabout 0.1% to about 50% by weight of at least one mid-chain branchedsurfactant selected from the group consisting of surfactants having theformula: ##STR50## wherein: (i) one or more C₁ -C₃ alkyl moieties branchfrom the longest linear carbon chain at the positions encompassed by theindicated branching range, with the proviso that said surfactants aresubstantially free of geminal branching; and(ii) B is a hydrophilicmoiety selected from sulfates, polyoxyalkylene, and alkoxylatedsulfates; and wherein further for this surfactant mixture the averagetotal number of carbon atoms in the branched primary alkyl moietieshaving the above formula is within the range of greater than 14.5 toabout 17.5; c) from about 0.1% to about 99.8% by weight of detergentcomposition adjunct ingredients; andwherein the composition has anin-use pH in the range of 9-11.
 10. A detergent composition according toclaim 9 wherein said mid-chain branched surfactant has B as sulfate andthe branching as methyl, and ##STR51## wherein the total number ofcarbon atoms in the branched primary alkyl moiety,including the [R, R¹,and R² ] branching, is from 14 to
 20. 11. A detergent compositionaccording to claim 9 wherein said mid-chain branched surfactant B asalkoxy and the branching as methyl, and ##STR52## wherein the totalnumber of carbon atoms in the branched primary alkyl moiety, includingthe [R, R¹, and R³ ] branching, but not including the carbon atoms inthe EO/PO alkoxy moiety, is from 14 to
 20. 12. A detergent compositionaccording to claim 9 wherein said mid-chain branched surfactant has B asalkoxysulfate and the branching as methyl and ##STR53## wherein thetotal number of carbon atoms in the branched primary alkyl moiety,including the [R, R¹, and R² ] branching, but not including the carbonatoms in the EO/PO alkoxy moiety, is from 14 to
 20. 13. A detergentcomposition comprising:a) from about 0.0001% to about 2% by weight ofactive detersive enzyme; b) from about 0.1% to about 50% by weight of atleast one mid-chain branched surfactant selected from the groupconsisting of surfactants having the formula: ##STR54## wherein: (i) oneor more C₁ -C₃ alkyl moieties branch from the longest linear carbonchain at the positions encompassed by the indicated branching range,with the proviso that said surfactants are substantially free of geminalbranching; and(ii) B is a hydrophilic moiety selected from sulfates,polyoxyalkylene and alkoxylated sulfates; and wherein further for thissurfactant mixture the average total number of carbon atoms in thebranched primary alkyl moieties having the above formula is within therange of greater than 14.5 to about 17.5; c) from about 0.1% to about99.8% by weight of detergent composition adjunct ingredients; andwhereinthe composition has an in-use pH in the range of 9-11.
 14. A detergentcomposition according to claim 13 wherein the active detersive enzyme isselected from the group consisting of proteases, cellulases, lipases,amylases, peroxidases, and mixtures thereof.